Inorganic substance layer-by-layer applied undercoat agent composition, cured product thereof, and manufacturing method thereof

Abstract

An inorganic substance layer-by-layer bottom coating agent composition, which is applied to a resin substrate in order to layer inorganic substances on the resin substrate by a dry film-forming method, and is characterized by containing a polysiloxane compound represented by the following formula (1), and a radical polymerization initiator and / or a cationic polymerization initiator. #imgabs0#

Description

Technical Field

[0001] The present disclosure relates to a primer composition for inorganic material layer-by-layer lamination, a cured product thereof, and a manufacturing method thereof, and to a laminate including a cured product for inorganic material layer-by-layer lamination, a resin substrate, and an inorganic material layer. More specifically, the present disclosure relates to a primer composition for inorganic material layer-by-layer lamination including a polysiloxane compound and a polymerization initiator. The cured product of the primer composition for inorganic material layer-by-layer lamination is useful as a primer for inorganic material layer-by-layer lamination when manufacturing, for example, a display substrate, a touch panel, a thin film with electrodes, and a lens, etc. Background Art

[0002] In recent years, it has been proposed to layer inorganic materials on the surface of a resin substrate by a dry film-forming method or the like in order to impart or improve various functions such as weather resistance, chemical resistance, hardness, scratch resistance, durability, heat resistance, conductivity, gas barrier property, antifouling property, and antireflection property.

[0003] Japanese Patent Application Laid-Open No. 2009-178904 discloses a decorative printed film laminate characterized by including: a plastic film having a glass transition temperature of 70°C or higher; a transparent resin layer formed by curing a photocurable resin composition on the plastic film, the photocurable resin composition containing a photocurable cage-type silsesquioxane resin; and a surface modification film layer laminated on the surface of the transparent resin layer by a sputtering method.

[0004] Japanese Patent Application Laid-Open No. 2010-274562 discloses a gas barrier laminate characterized by having a combination of one or more organic compound layers, a layer containing polysilsesquioxane formed thereon, and an oxide inorganic compound layer formed thereon by chemical vapor deposition.

[0005] Japanese Patent Application Laid-Open No. 2013-035274 discloses a laminate characterized by having a cured coating film layer formed of an active energy ray-curable primer composition and an inorganic material layer formed of a silicon oxide compound by a dry film-forming method laminated in this order on a polycarbonate resin substrate, the active energy ray-curable primer composition containing a (meth)acryloyloxy group-containing silsesquioxane compound, a photopolymerization initiator, and an unsaturated group-containing silicon-based surface modifier. Summary of the Invention

[0006] However, when the cured product of a composition containing silsesquioxane is used as a primer layer as disclosed in Japanese Patent Application Laid-Open No. 2009-178904, Japanese Patent Application Laid-Open No. 2010-274562, and Japanese Patent Application Laid-Open No. 2013-035274, the adhesion to the inorganic material layer laminated thereon is still insufficient, and there are practical problems.

[0007] According to an embodiment of the present disclosure, there is provided an undercoat agent composition for laminating an inorganic material layer, a cured product thereof, a laminate using the same, and a method for manufacturing the same, which can provide a cured product (primer layer) having good adhesion to an inorganic material layer laminated by a dry film-forming method.

[0008] The present disclosure includes the following aspects [1] to

[11] .

[0009] [1] An undercoat agent composition for laminating an inorganic material layer, which is coated on a resin substrate in order to laminate an inorganic material layer on the resin substrate by a dry film-forming method, and is characterized by containing a polysiloxane compound represented by the following formula (1), a radical polymerization initiator, and / or a cationic polymerization initiator.

[0010] [Chemical formula 1]

[0011]

[0012] In formula (1), R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a monovalent organic group having a (meth)acryloyl group, an epoxy group, or an oxetanyl group, and the alkyl group, aralkyl group, aryl group, unsaturated hydrocarbon group, (meth)acryloyl group, epoxy group, and oxetanyl group may be substituted by at least one selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyl group, and an oxy group. Among R 1 , R 2 and R 3 , at least one is a monovalent organic group having a (meth)acryloyl group, an epoxy group, or an oxetanyl group. R 1 , R 2 and R 3 may be the same as or different from each other. In formula (1), v, w, x, and y respectively represent the proportions of v, w, x, and y in the total amount, w represents a positive number of 1 or less, and v, x, and y each independently represent 0 or a positive number less than 1.

[0013] [2] The undercoat agent composition for laminating an inorganic material layer according to [1] above, wherein x in formula (1) is a positive number.

[0014] [3] The undercoat agent composition for laminating an inorganic material layer according to [1] or [2] above, wherein the dry film-forming method is a physical vapor deposition method.

[0015] [4] The inorganic substance layer-by-layer bottom coating agent composition according to any one of [1] to [3] above satisfies 0.3 ≤ {w / (v + w + x + y)} ≤ 1.0 and 0 ≤ {x / (v + w + x + y)} ≤ 0.7.

[0016] [5] The inorganic substance layer-by-layer bottom coating agent composition according to any one of [1] to [3] above satisfies 0.5 ≤ {w / (v + w + x + y)} ≤ 1.0 and 0 ≤ {y / (v + w + x + y)} ≤ 0.5.

[0017] [6] The inorganic substance layer-by-layer bottom coating agent composition according to any one of [1] to [5] above, wherein the viscosity of the polysiloxane compound at 25°C is 10 to 1,000,000 mPa·s.

[0018] [7] A cured product for inorganic substance layer-by-layer lamination, which is obtained by curing the inorganic substance layer-by-layer bottom coating agent composition according to any one of [1] to [6] above.

[0019] [8] A laminate, comprising the cured product for inorganic substance layer-by-layer lamination according to [7] above, a resin substrate, and an inorganic substance layer.

[0020] [9] In the evaluation of the adhesion of the inorganic substance layer to the cured product for inorganic substance layer-by-layer lamination in the cross-cut peel test according to the laminate of [8] above, the number of peeled squares is 5 or less out of 25 squares.

[0021]

[10] A method for manufacturing the cured product for inorganic substance layer-by-layer lamination according to [7] above, comprising the step of irradiating the inorganic substance layer-by-layer bottom coating agent composition according to any one of [1] to [6] above with active energy rays and curing it.

[0022]

[11] A method for manufacturing the laminate according to [8] or [9] above, comprising the step of irradiating the inorganic substance layer-by-layer bottom coating agent composition according to any one of [1] to [6] above with active energy rays and curing it.

[0023] According to an embodiment of the present disclosure, there is provided an inorganic substance layer-by-layer bottom coating agent composition, a cured product thereof, a laminate using the same, and a manufacturing method thereof, which can provide a cured product (primer layer) having good adhesion to an inorganic substance layer laminated by a dry film forming method. Detailed Description

[0024] Hereinafter, the present disclosure will be described in detail.

[0025] It should be noted that unless otherwise specified, "%" means "wt%", "parts" means "parts by weight", and "ppm" means "weight ppm". In addition, in the present disclosure, the description of "lower limit to upper limit" representing a numerical range means "equal to or higher than the lower limit and equal to or lower than the upper limit", and the description of "upper limit to lower limit" means "equal to or lower than the upper limit and equal to or higher than the lower limit". That is, it represents a numerical range including the upper and lower limits. Furthermore, in the present disclosure, combinations of two or more of the preferred aspects described later are also preferred aspects.

[0026] Hereinafter, a polysiloxane compound, a polymerization initiator, an inorganic substance layer-by-layer bottom coating agent composition, a cured product, a laminate, and a method for producing the cured product and the laminate will be described.

[0027] 1. Polysiloxane compound

[0028] The polysiloxane compound according to the present disclosure is a polysiloxane compound represented by the following formula (1), and the polysiloxane compound has at least a (meth)acryloyl group, an epoxy group, or an oxetanyl group, and w is a positive number of 1 or less.

[0029] Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group, and the same meaning applies hereinafter.

[0030] [Chemical formula 2]

[0031]

[0032] Each structural unit that the polysiloxane compound according to the present disclosure can have is referred to as structural units (a) to (d), and will be described hereinafter.

[0033] Structural unit (a): (SiO 4 / 2 ) v

[0034] [Chemical formula 3]

[0035]

[0036] Structural unit (b): (R 1 SiO 3 / 2 ) w

[0037] [Chemical formula 4]

[0038]

[0039] Structural unit (c): (R 2 2SiO 2 / 2 ) x

[0040] [Chemical formula 5]

[0041]

[0042] Structural unit (d): (R 3 3SiO 1 / 2 ) y

[0043] [Chemical formula 6]

[0044]

[0045] The polysiloxane compound involved in the present disclosure can include the above-mentioned structural units (a) to (d).

[0046] In formula (1), v, w, x, and y respectively represent the proportions of v, w, x, and y in the total amount. w represents a positive number not exceeding 1, and v, x, and y each independently represent 0 or a positive number less than 1.

[0047] That is, v, w, x, and y in formula (1) represent the molar ratios of each structural unit in the structural units (a) to (d). In other words, as described below.

[0048] v / (v + w + x + y) represents the molar ratio of structural unit (a) in the structural units (a) to (d),

[0049] w / (v + w + x + y) represents the molar ratio of structural unit (b) in the structural units (a) to (d),

[0050] x / (v + w + x + y) represents the molar ratio of structural unit (c) in the structural units (a) to (d),

[0051] y / (v + w + x + y) represents the molar ratio of structural unit (d) in the structural units (a) to (d).

[0052] It should be noted that in formula (1), v, w, x, and y represent the relative molar ratios of the respective structural units contained in the polysiloxane compound involved in the present disclosure represented by formula (1). That is, the molar ratio is the relative ratio of the number of repetitions of each structural unit represented by formula (1). The molar ratio can be obtained from the NMR analysis values of the polysiloxane compound involved in the present disclosure. In addition, when the reaction rates of the respective raw materials of the polysiloxane compound involved in the present disclosure are clear, or when the yield is 100%, the addition amounts of the raw materials can be obtained.

[0053] For each of the structural units (a), (b), (c), and (d) in formula (1), the corresponding structural unit can be only one kind, or two or more kinds. For example, there can be one kind of structural unit corresponding to structural unit (a), or two or more kinds. In addition, the arrangement order in formula (1) represents the composition of the structural units, rather than their arrangement order. Therefore, the condensation form of the structural units in the polysiloxane compound involved in the present disclosure does not necessarily have to be the same as the arrangement in formula (1).

[0054] 1-1. Structural unit (a): (SiO 4 / 2 ) v

[0055] The structural unit (a) is a so-called Q unit having four O's (two as oxygen atoms) relative to one silicon atom. It should be noted that the Q unit refers to a unit having four O's relative to one silicon atom. 1 / 2 (two as oxygen atoms) of the so-called Q unit. It should be noted that the Q unit refers to a unit having four O's relative to one silicon atom. 1 / 2 units.

[0056] The ratio of the structural unit (a) in the polysiloxane compound involved in the present disclosure, that is, (v / (v + w + x + y)), is 0 or a positive number less than 1. Considering the viscosity of the polysiloxane compound involved in the present disclosure and the softness of its cured product, the molar ratio (v / (v + w + x + y)) in the structural units (a) to (d) is preferably 0.6 or less, more preferably 0.3 or less, and still more preferably 0. Here, a molar ratio of 0 means that the structural unit is not included, and the same meaning applies hereinafter.

[0057] 1-2. Structural unit (b): (R 1 SiO 3 / 2 ) w

[0058] The structural unit (b) is a T unit having three O's (1.5 as oxygen atoms) relative to one silicon atom, and has an R bonded to the silicon atom. 1 / 2 (1.5 as oxygen atoms) of the T unit, and has an R bonded to the silicon atom. 1 .

[0059] R 1 represents a monovalent organic group, and the monovalent organic group has an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a (meth)acryloyl group, an epoxy group, or an oxetanyl group.

[0060] The alkyl group, aralkyl group, aryl group, unsaturated hydrocarbon group, (meth)acryloyl group, epoxy group, and oxetanyl group may be substituted with at least one selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyl group, and an oxy group.

[0061] The R, R, and R in the polysiloxane compound represented by formula (1) 1 , R 2 and R 3wherein at least one is a monovalent organic group having an (meth)acryloyl group, an epoxy group, or an oxetanyl group, R 1 , R 2 and R 3 may be the same as or different from each other. In the case where there are a plurality of groups corresponding to R 1 in one molecule, the plurality of R 1 may be the same as or different from each other.

[0062] In addition, among R 1 , R 2 and R 3 in the polysiloxane compound represented by the formula (1), at least one is a monovalent organic group having an (meth)acryloyl group, an epoxy group, or an oxetanyl group, preferably at least one is a monovalent organic group having an (meth)acryloyl group or an oxetanyl group, more preferably at least one is a monovalent organic group having an acryloyl group or an oxetanyl group, and still more preferably at least one is a monovalent organic group having an acryloyl group.

[0063] The alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, and the unsaturated hydrocarbon group having 2 to 8 carbon atoms in R 1 may be linear, branched, or may have a ring structure.

[0064] As the alkyl group having 1 to 10 carbon atoms in R 1 , there is no particular limitation, and it is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0065] As the aralkyl group having 7 to 10 carbon atoms in R 1 , there is no particular limitation, and it is preferably a phenylalkyl group, and more preferably a benzyl group.

[0066] As the aryl group having 6 to 10 carbon atoms in R 1 , there is no particular limitation, and it is preferably a phenyl group.

[0067] As the unsaturated hydrocarbon group having 2 to 8 carbon atoms in R 1 , there is no particular limitation, and it is preferably a vinyl group, an allyl group, an ethynyl group, or a styryl group, and more preferably a vinyl group.

[0068] As the monovalent organic group containing the (meth)acryloyl group in R 1 , there is no particular limitation, and it is preferably a group represented by the following formula (2). It should be noted that in the present disclosure, the “(meth)acryloyl group” means both an acryloyl group and a methacryloyl group.

[0069] [Chemical formula 7]

[0070]

[0071] In formula (2), R 4 represents a hydrogen atom or a methyl group, R 5 represents an alkylene group having 1 to 10 carbon atoms, and ※ represents a bonding site.

[0072] As R 5 in formula (2), there is no particular limitation, and it is preferably an alkylene group having 2 to 8 carbon atoms, more preferably a propylene group.

[0073] As a monovalent organic group containing an epoxy group in R 1 , there is no particular limitation, and it is preferably a glyceroxyalkyl group, more preferably a glycidyloxypropyl group.

[0074] As a monovalent organic group containing an oxetanyl group in R 1 , there is no particular limitation, and it is preferably a group represented by the following formula (3).

[0075] [Chemical formula 8]

[0076]

[0077] In formula (3), R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 7 represents an alkylene group having 1 to 10 carbon atoms, and ※ represents a bonding site.

[0078] As R 6 in formula (3), there is no particular limitation, and it is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably an ethyl group.

[0079] As R 7 in formula (3), there is no particular limitation, and it is preferably an alkylene group having 2 to 8 carbon atoms, more preferably a propylene group.

[0080] The proportion of the structural unit (b) in the polysiloxane compound according to the present disclosure is not particularly limited, but considering the weather resistance, chemical resistance, hardness, scratch resistance, durability, heat resistance and / or oxidation resistance of the polysiloxane compound and its cured product according to the present disclosure, the molar ratio (w / (v + w + x + y)) in the structural units (a) to (d) is a positive number of 1 or less, preferably 0.3 to 1.0, more preferably 0.5 to 0.95, and further preferably 0.6 to 0.9.

[0081] 1-3. Structural unit (c): (R 2 2SiO 2 / 2 ) x

[0082] The structural unit (c) is a so-called D unit having two O 1 / 2 (one as an oxygen atom) relative to one silicon atom. It should be noted that the D unit refers to a unit having two O 1 / 2 relative to one silicon atom.

[0083] R 2 each independently represents a monovalent organic group having an alkyl group with 1 to 10 carbon atoms, an aralkyl group with 7 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an unsaturated hydrocarbon group with 2 to 8 carbon atoms, or a (meth)acryloyl group, an epoxy group or an oxetanyl group.

[0084] The alkyl group, aralkyl group, aryl group, unsaturated hydrocarbon, (meth)acryloyl group, epoxy group and oxetanyl group may be substituted with at least one selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyl group, and an oxy group.

[0085] R in the polysiloxane compound represented by the formula (1) 1 , R 2 and R 3 Among them, at least one is a monovalent organic group having a (meth)acryloyl group, an epoxy group or an oxetanyl group, and R 1 , R 2 and R 3 may be the same as or different from each other, and R in one molecule 2 may be the same as or different from each other. Examples of these substituents include the same substituents as those exemplified for R 1 of the aforementioned structural unit (b).

[0086] Since the structural unit (c) is a D unit, it contributes to the reduction of the viscosity of the polysiloxane compound according to the present disclosure and the improvement of the flexibility, heat resistance and / or oxidation resistance of its cured product.

[0087] From the viewpoints of heat resistance, ease of obtaining raw materials, and imparting flexibility to the cured product, R 2 are each independently preferably a methyl group or a phenyl group, more preferably a methyl group.

[0088] The ratio of the structural unit (c) in the polysiloxane compound according to the present disclosure, that is, (x / (v + w + x + y)), is 0 or a positive number less than 1. Considering the reduction of the viscosity of the polysiloxane compound according to the present disclosure and the hardness, scratch resistance, weather resistance and / or flexibility of its cured product, the molar ratio (x / (v + w + x + y)) in the structural units (a) to (d) is preferably 0 ≤ {x / (v + w + x + y)} ≤ 0.7, more preferably 0.05 to 0.6, and further preferably 0.1 to 0.5. However, when x = 0, at least one of R 1 in the aforementioned structural unit (b) and R 3 in the structural unit (d) described later is a monovalent organic group having a (meth)acryloyl group, an epoxy group, or an oxetanyl group.

[0089] In particular, when the value of x / (v + w + x + y) is in the range of 0.05 to 0.6, the adhesion to the inorganic material layer of the cured product is particularly good, and the inorganic material layer of the obtained laminate also shows good abrasion resistance. Since these two physical properties can be balanced, this is preferred.

[0090] 1-4. Structural unit (d): (R 3 3SiO 1 / 2 ) Z

[0091] The structural unit (d) has one O 1 / 2 (0.5 as an oxygen atom), which is a so-called M unit. It should be noted that the M unit refers to a unit having one O 1 / 2 per silicon atom.

[0092] R 3 each independently represents a monovalent organic group, and the monovalent organic group has an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a (meth)acryloyl group, an epoxy group, or an oxetanyl group.

[0093] The alkyl group, aralkyl group, aryl group, unsaturated hydrocarbon group, (meth)acryloyl group, epoxy group, and oxetanyl group may be substituted with at least one selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyl group, and an oxy group.

[0094] In the polysiloxane represented by the formula (1), at least one of R 1 , R 2 and R 3 is a monovalent organic group having a (meth)acryloyl group, an epoxy group, or an oxetanyl group. R 1 , R 2 and R 3 may be the same as or different from each other, and R 3 in one molecule may be the same as or different from each other. Examples of these substituents include the same substituents as those exemplified for R 1 of the aforementioned structural unit (b).

[0095] Since the structural unit (d) is an M unit, it contributes to the reduction of the viscosity of the polysiloxane compound according to the present disclosure and the improvement of the softness of the cured product.

[0096] From the viewpoints of heat resistance, ease of obtaining raw materials, curability of the undercoat agent composition, and / or imparting softness to the cured product, R 3 are each independently preferably a methyl group, a phenyl group, or a vinyl group, and more preferably a methyl group or a vinyl group.

[0097] The ratio of the structural unit (d) in the polysiloxane compound according to the present disclosure, i.e., (y / (v + w + x + y)), is 0 or a positive number less than 1. Considering the reduction of the viscosity of the polysiloxane compound according to the present disclosure and the hardness, weather resistance, and / or flexibility of its cured product, the molar ratio (y / (v + w + x + y)) in the structural units (a) to (d) is preferably 0 ≤ {y / (v + w + x + y)} ≤ 0.5, more preferably 0 to 0.4, and still more preferably 0 to 0.3. However, when y = 0, R in the aforementioned structural unit (b) 1 and R in the aforementioned structural unit (c) 2 at least one of them is a monovalent organic group having a (meth)acryloyl group, an epoxy group, or an oxetanyl group.

[0098] 1-5. Other structural units (e)

[0099] The polysiloxane compound according to the present disclosure may further include (R 8 O 1 / 2 ) as a Si-free structural unit (hereinafter referred to as structural unit (e)).

[0100] Among them, R 8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be either an aliphatic group or an alicyclic group, and may be either linear or branched. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0101] This structural unit is an alkoxy group as a hydrolyzable group contained in the raw material monomer described later, or an alkoxy group formed by substituting the alcohol contained in the reaction solvent with the hydrolyzable group of the raw material monomer, and is a group remaining in the molecule without hydrolysis and polycondensation, or a hydroxyl group remaining in the molecule without polycondensation after hydrolysis.

[0102] 1-6. Molecular weight, etc.

[0103] The weight average molecular weight (hereinafter also referred to as "Mw") of the polysiloxane compound according to the present disclosure is not particularly limited, and is preferably in the range of 300 to 10,000. The polysiloxane compound itself is a liquid, has a low viscosity suitable for processing, is easily soluble in organic solvents, the viscosity of its solution is also easy to handle, and its storage stability is excellent. Mw is more preferably 500 to 8,000, still more preferably 600 to 7,000, and particularly preferably 700 to 6,000.

[0104] It should be noted that Mw in the present disclosure refers to a value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. For example, under the measurement conditions in the [Examples] described later, Mw can be determined.

[0105] The state of the polysiloxane compound involved in the present disclosure is not particularly limited, and examples thereof include liquids, solids, and semi-solids. The polysiloxane compound involved in the present disclosure is preferably a liquid, and its viscosity is not particularly limited. For example, the viscosity at 25 °C is preferably 10 to 1,000,000 mPa·s, more preferably 100 to 100,000 mPa·s, further preferably 300 to 30,000 mPa·s, still further preferably 400 to 10,000 mPa·s, and particularly preferably 500 to 5,000 mPa·s. In particular, when it is 10,000 mPa·s or less, the workability such as coating in a solvent-free system is excellent, and in addition, no organic solvent is discharged into the environment, and the environmental resistance is also excellent, so it is preferred. In addition, if the viscosity is low, the surface of the undercoat layer for laminating inorganic substances that is easily cured by coating becomes smooth, and it is also preferred for laminating inorganic substances.

[0106] It should be noted that in the present disclosure, the viscosity refers to the value measured at 25 °C using an E-type viscometer (cone-plate viscometer. For example, the TVE22H type viscometer manufactured by Toki Sangyo Co., Ltd.).

[0107] 2. Method for producing the polysiloxane compound according to the present disclosure

[0108] The polysiloxane compound involved in the present disclosure can be produced by a known method. The production method of the polysiloxane compound is not particularly limited. For example, the production method of polysiloxane is disclosed in detail in Japanese Patent Laid-Open No. 11-116682, Japanese Patent Laid-Open No. 2000-044689, WO2004 / 076534 International Publication Pamphlet, WO2009 / 090916 International Publication Pamphlet, WO2009 / 131038 International Publication Pamphlet, WO2012 / 090707 International Publication Pamphlet, WO2013 / 031798 International Publication Pamphlet, etc.

[0109] The polysiloxane compound involved in the present disclosure can be produced, for example, by the following method.

[0110] That is, the manufacturing method of the polysiloxane compound according to the present disclosure can include a condensation step, in which hydrolysis and polycondensation reactions of the raw material monomers that impart the structural units in the formula (1) are carried out by condensation using an appropriate acid or base as a reaction catalyst in an appropriate reaction solvent. In this condensation step, for example, a silicon compound having four siloxane bond-forming groups that forms the structural unit (a) (Q unit) (hereinafter referred to as "Q monomer"), a silicon compound having three siloxane bond-forming groups that forms the structural unit (b) (T unit) (hereinafter referred to as "T monomer"), a silicon compound having two siloxane bond-forming groups that forms the structural unit (c) (D unit) (hereinafter referred to as "D monomer"), and a silicon compound that forms the structural unit (d) (M unit) having one siloxane bond-forming group (hereinafter referred to as "M monomer") can be used.

[0111] The manufacturing method of the polysiloxane compound according to the present disclosure preferably includes a distillation removal step, in which the raw material monomers are subjected to hydrolysis and polycondensation reactions in the presence of a reaction solvent, and then the reaction solvent, by-products, residual monomers, water, etc. in the reaction solution are distilled off. In addition, a cleaning step of cleaning the reaction solution and the reaction concentrate with water or the like can also be appropriately provided.

[0112] 2-1. Raw material monomers

[0113] The siloxane bond-forming groups contained in the raw material monomers, namely Q monomer, T monomer, D monomer and M monomer, are hydroxyl groups and / or hydrolyzable groups. Among them, examples of the hydrolyzable group include halogenated groups, alkoxy groups, and silyloxy groups. In the condensation step, from the viewpoints of good hydrolysis and no acid generation, the hydrolyzable group is preferably an alkoxy group, and more preferably an alkoxy group having 1 to 3 carbon atoms. In addition, in the M monomer, from the viewpoint of easy availability of the raw material, the hydrolyzable group is preferably a silyloxy group, and a disiloxane composed of two structural units (d) can be used.

[0114] In the condensation step, the siloxane bond-forming groups of the Q monomer, T monomer and D monomer corresponding to each structural unit are preferably alkoxy groups, and the siloxane bond-forming group contained in the M monomer is preferably an alkoxy group or a silyloxy group. In addition, each monomer corresponding to the structural unit can be used alone or in combination of two or more.

[0115] Examples of the Q monomer that imparts the structural unit (a) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

[0116] Examples of the T monomer for imparting the structural unit (b) include trimethoxyvinylsilane, triethoxyvinylsilane, vinyltrichlorosilane, allyltrimethoxysilane, ethynyltriethoxysilane, (p-styryl)trimethoxysilane, (p-styryl)triethoxysilane, (3-methacryloxypropyl)trimethoxysilane, (3-methacryloxypropyl)triethoxysilane, (3-acryloxypropyl)trimethoxysilane, (3-acryloxypropyl)triethoxysilane, (8-methacryloxyoctyl)trimethoxysilane, (8-acryloxyoctyl)trimethoxysilane, 3-ethyl-3-[(3-(trimethoxysilyl)propoxy)methyl]oxetane, 3-ethyl-3-[(3-(triethoxysilyl)propoxy)methyl]oxetane, 3-[3-(triethoxysilyl)propoxy]oxetane, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, {2-(3,4-epoxycyclohexyl)ethyl}trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, benzyltriethoxysilane, and benzyltrichlorosilane, etc.

[0117] Examples of the D monomer for imparting the structural unit (c) include dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, dichloromethylvinylsilane, dimethoxyallylmethylsilane, dimethoxyallylethylsilane, diethoxyethynylmethylsilane, diethoxyethynylethylsilane, (p-styryl)dimethoxymethylsilane, (p-styryl)dimethoxyethylsilane, (p-styryl)diethoxymethylsilane, (3-methacryloxypropyl)dimethoxymethylsilane, (3-methacryloxypropyl)diethoxymethylsilane, (3-methacryloxypropyl)diethoxymethylsilane, (3-methacryloxypropyl)diethoxyethylsilane, (3-acryloxypropyl)dimethoxymethylsilane, (3-acryloxypropyl)diethoxymethylsilane, (8-methacryloxyoctyl)dimethoxymethylsilane, (8-acryloxyoctyl)dimethoxymethylsilane, 3-ethyl-3-[(3-(dimethoxymethylsilyl)propoxy)methyl]oxetane, 3-ethyl-3-[(3-(diethoxymethylsilyl)propoxy)methyl]oxetane, 3-[3-(diethoxymethylsilyl)propoxy]oxetane, (3-glycidoxypropyl)dimethoxymethylsilane, (3-glycidoxypropyl)dimethoxyethylsilane, (3-glycidoxypropyl)diethoxymethylsilane, {2-(3,4-epoxycyclohexyl)ethyl}dimethoxymethylsilane, dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, diisopropoxydimethylsilane, dichlorodimethylsilane, diethoxymethylpropylsilane, dimethoxybutylmethylsilane, diethoxyoctylmethylsilane, dimethoxydecylmethylsilane, dimethoxycyclohexylmethylsilane, diethoxycyclohexylmethylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, dichloromethylphenylsilane, dimethoxybenzylmethylsilane, diethoxybenzylmethylsilane, and dichlorobenzylmethylsilane, etc.

[0118] Furthermore, D unit oligomers having a silanol group and / or an alkoxysilyl group capable of undergoing hydrolysis and condensation reactions, i.e., so-called silicones, can also be used as the D monomer for imparting the structural unit (c) in the present disclosure and used as a raw material for producing the polysiloxane compound represented by the formula (1). Examples include terminal silanol type dimethyl silicone, terminal methoxy type dimethyl silicone, dimethyl silicone having both silanol and methoxy at the terminal, terminal silanol type methylphenyl silicone, terminal methoxy type methylphenyl silicone, and methylphenyl silicone having both silanol and methoxy at the terminal, etc., and their molecular weights can be arbitrarily selected. In addition, these raw material silicones may also contain cyclic siloxanes.

[0119] As the M monomer that imparts the structural unit (d), in addition to hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane that impart two structural units (d) through hydrolysis, examples include methoxytrimethylsilane, ethoxytrimethylsilane, propoxytrimethylsilane, isopropoxytrimethylsilane, ethoxydimethylethylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, dimethyvinylchlorosilane, trimethylchlorosilane, dimethyvinylsilanol, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, ethoxydimethylpropylsilane, methoxybutyldimethylsilane, ethoxyoctyldimethylsilane, methoxydecyldimethylsilane, methoxycyclohexyldimethylsilane, methoxybenzyldimethylsilane, benzyldimethylchlorosilane, methoxydimethyvinylsilane, methoxydiethyvinylsilane, ethoxydimethyvinylsilane, dimethyvinylchlorosilane, methoxyallyldimethylsilane, ethoxyethynyldimethylsilane, (p-styryl)methoxydimethylsilane, (p-styryl)ethoxydimethylsilane, (3-methacryloxypropyl)methoxydimethylsilane, (3-methacryloxypropyl)ethoxydimethylsilane, (3-acryloxypropyl)methoxydimethylsilane, (3-acryloxypropyl)ethoxydimethylsilane, (8-methacryloxyoctyl)methoxydimethylsilane, (8-acryloxyoctyl)methoxydimethylsilane, 3-ethyl-3-[{3-(methoxydimethylsilyl)propoxy}methyl]oxetane, 3-ethyl-3-[{3-(ethoxydimethylsilyl)propoxy}methyl]oxetane, 3-{3-(ethoxydimethylsilyl)propoxy}oxetane, (3-glycidoxypropyl)methoxydimethylsilane, (3-glycidoxypropyl)ethoxydimethylsilane, and {2-(3,4-epoxycyclohexyl)ethyl}methoxydimethylsilane, etc.

[0120] As the compound that reacts with the raw material monomer to impart the structural unit (e), examples include water, and alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol.

[0121] The feeding ratios of the Q monomer, T monomer, D monomer, and M monomer as the raw material monomers can be appropriately set as long as they are based on the values of v to y of the target formula (1) in the polysiloxane compound related to the present disclosure.

[0122] In addition, the polysiloxane compound represented by the formula (1) may contain a group obtained by ring-opening of an oxetanyl group and an epoxy group by addition of an acid or the like in the side-chain functional groups derived from the monomers used in the production, may contain a hydroxyalkyl group generated by decomposition of a monovalent organic group having a (meth)acryloyl group, or may contain a group obtained by addition of an acid or the like to an unsaturated hydrocarbon group or the like. As a specific example thereof, for example, it is an example in which a structure represented by the following formula (A) and / or a structure represented by the formula (B) is contained in a part of the formula (1). As its content, it is sufficient that it is 50 mol% or less, preferably 30 mol% or less, and more preferably 10 mol% or less of the original monovalent organic group having an oxetanyl group or the monovalent organic group having a (meth)acryloyl group derived from the raw material. Both the formula (A) and the formula (B) illustrate the T unit, but similarly, it may also be the D unit and the M unit.

[0123] [Chemical formula 9]

[0124]

[0125] [Chemical formula 10]

[0126]

[0127] 2-2. Reaction solvent

[0128] In the condensation step, an alcohol can be used as the reaction solvent. The alcohol is a narrow-sense alcohol represented by the general formula R-OH and is a compound having no functional group other than an alcoholic hydroxyl group.

[0129] The alcohol is not particularly limited, and as specific examples thereof, methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, cyclohexanol, and secondary or tertiary alcohols having 7 to 10 carbon atoms can be exemplified. Among these, secondary alcohols such as 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, and cyclohexanol are preferably used.

[0130] In the condensation step, one or more of these alcohols can be used in combination. A more preferable alcohol is a compound capable of dissolving water at the concentration required in the condensation step. An alcohol having such a property is a compound having a water solubility of 10 g or more per 100 g of alcohol at 20°C.

[0131] Using an alcohol used in the condensation step in an amount of 0.5% by mass or more based on the total amount of all reaction solvents, including the additional input amount during the hydrolysis and polycondensation reactions, can suppress the gelation of the polysiloxane compound according to the present disclosure. The preferred usage amount is 1% by mass or more and 60% by mass or less, and more preferably 3% by mass or more and 40% by mass or less.

[0132] The reaction solvent used in the condensation step can be only an alcohol or a mixed solvent with at least one co-solvent. The co-solvent is either a polar solvent or a non-polar solvent, or a combination of both. As the polar solvent, glycols, ethers, amides, ketones, esters, and cellosolves having 2 to 20 carbon atoms are preferred.

[0133] The non-polar solvent is not particularly limited, and examples include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and chlorinated hydrocarbons. The non-polar solvent is not particularly limited. For example, n-hexane, iso-hexane, cyclohexane, heptane, toluene, xylene, and dichloromethane are azeotropic with water, and thus are preferred. If these compounds are used in combination, after the condensation step, when removing the reaction solvent from the reaction mixture containing the polysiloxane compound by distillation, water can be efficiently distilled off. From the perspective of a higher boiling point, xylene, an aromatic hydrocarbon, is particularly preferred as the non-polar solvent.

[0134] 2-3. Water and catalyst for hydrolysis reaction

[0135] The hydrolysis and polycondensation reactions in the condensation step are carried out in the presence of water.

[0136] The amount of water for hydrolyzing the hydrolyzable groups contained in the raw material monomers is preferably 0.5 to 5 times the molar amount, and more preferably 1 to 2 times the molar amount, relative to the hydrolyzable groups.

[0137] In addition, the hydrolysis and polycondensation reactions of the raw material monomers can be carried out without a catalyst or with a catalyst. When using a catalyst, an acid catalyst or a base catalyst can generally be used. There is no particular limitation on the acid catalyst, and examples include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; and organic acids such as formic acid, acetic acid, oxalic acid, and toluenesulfonic acid. There is no particular limitation on the base catalyst, and examples include ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

[0138] The usage amount of the catalyst is preferably an amount equivalent to 0.01 to 20 mol%, and more preferably an amount equivalent to 0.1 to 10 mol%, relative to the total amount of silicon atoms contained in the raw material monomers.

[0139] 2-4. Other additives

[0140] The completion of the hydrolysis and polycondensation reactions in the condensation step can be appropriately detected by the methods described in various bulletins and the like. It should be noted that in the condensation step of manufacturing the polysiloxane compound according to the present disclosure, an auxiliary agent can be added to the reaction system.

[0141] Examples of the auxiliary agent include an antifoaming agent that suppresses foaming of the reaction liquid, a scale control agent that prevents scale from adhering to the reaction tank or the stirring shaft, and a polymerization inhibitor. The usage amount of these auxiliary agents is arbitrary, but it is preferably about 1 to 100% by weight relative to the concentration of the polysiloxane compound according to the present disclosure in the reaction mixture.

[0142] 2-5. Distillation removal of reaction solvent, etc.

[0143] By providing a distillation removal step after the condensation step in the manufacturing of the polysiloxane compound according to the present disclosure, the stability of the produced polysiloxane compound according to the present disclosure can be improved. The distillation removal step is to distill and remove the reaction solvent, by-products, residual monomers, water, and catalyst contained in the reaction liquid obtained from the condensation step. The distillation removal can usually be carried out under normal pressure or reduced pressure, and can usually be carried out at normal temperature or under heating, or can also be carried out under cooling.

[0144] In addition, before distilling off the reaction solvent and the like, the residual catalyst can be neutralized. The solvent and the like can be distilled off after washing the reaction liquid or the neutralized reaction liquid, or washing can be carried out after concentrating the reaction liquid or the neutralized reaction liquid. For washing, commonly used aqueous media such as pure water and saturated brine can be used.

[0145] 3. Polymerization initiator

[0146] There is no particular limitation on the polymerization initiator contained in the undercoat agent composition for laminating inorganic substances according to the present disclosure, and known polymerization initiators used in polymerization reactions can be used, and a photoinitiator and / or a thermal polymerization initiator can be arbitrarily selected according to the usage situation. Since the polysiloxane compound represented by the formula (1) cures in a relatively short time, from the viewpoint of productivity, a photoinitiator is more preferred.

[0147] When the polymerizable group is a radical polymerizable group such as (meth)acryloyl, a radical polymerization initiator is preferably used, and when the polymerizable group is a cationic polymerizable group such as oxetanyl and epoxy group, a cationic polymerization initiator is preferably used.

[0148] The amount of the polymerization initiator contained in the undercoat agent composition for laminating inorganic substances according to the present disclosure is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and further preferably 1 to 5 parts by weight, based on 100 parts by weight of the polysiloxane compound represented by the formula (1).

[0149] 3-1. Actinic energy ray radical polymerization initiator

[0150] The living energy ray radical polymerization initiator used in the present disclosure is not particularly limited, and examples thereof include acetophenone compounds such as benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]acetone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one; benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1-[4-(4-benzoylphenylthio)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; and thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and fluorothioxanthone, etc.

[0151] As compounds other than the above, examples include benzyl, ethyl(2,4,6-trimethylbenzoyl)phenylphosphite, methyl phenylglyoxylate, ethyl anthraquinone, phenanthraquinone, and camphorquinone, etc.

[0152] These can be used alone or in combination of two or more.

[0153] 3-2. Thermal radical polymerization initiator

[0154] The thermal radical polymerization initiator used in the present disclosure is not particularly limited, and examples thereof include peroxides and azo initiators.

[0155] As specific examples of the peroxide, hydrogen peroxide can be cited; inorganic peroxides such as sodium persulfate, ammonium persulfate, potassium persulfate; 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-di(butylperoxycyclohexyl))propane, 1,1-bis(tert-butylperoxy)cyclododecane, tert-hexylperoxy isopropyl carbonate, tert-butylperoxy maleic acid, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butyl peroxy laurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, tert-hexylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peroxyacetate, 2,2-bis(tert-butylperoxy)butane, tert-butyl peroxybenzoate, n-butyl-4,4-bis(tert-butylperoxy)valerate, di(tert-butyl) phthalate, α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, terpinyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, tert-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide and other organic peroxides.

[0156] These can be used alone or in combination of two or more.

[0157] As specific examples of the azo initiator, azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane can be cited. These can be used alone or in combination of two or more.

[0158] In addition, the redox reaction can also be carried out by combining with a redox polymerization initiation system using a peroxide and a reducing agent, and the reducing agent is ascorbic acid, sodium ascorbate, sodium isoascorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, ferric chloride, etc.

[0159] 3-3. Actinic energy ray cationic polymerization initiator

[0160] The cationic polymerization initiator for active energy rays used in the present disclosure is not particularly limited, and examples thereof include onium salts such as iodonium salts, sulfonium salts, diazonium salts, selenonium salts, pyridinium salts, ferrocenium salts, and phosphonium salts. Among these, iodonium salts and sulfonium salts are preferred.

[0161] When the cationic polymerization initiator for active energy rays is an iodonium salt or a sulfonium salt, examples of the counter anion include BF4 - , AsF6 - , SbF6 - , PF6 - and B(C6F5)4 - etc.

[0162] Examples of the iodonium salt include (trialkyl)iodonium-tetrakis(pentafluorophenyl)borate, diphenyliodonium-hexafluorophosphate, diphenyliodonium-hexafluoroantimonate, diphenyliodonium-tetrafluoroborate, diphenyliodonium-tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium-hexafluorophosphate, bis(dodecylphenyl)iodonium-hexafluoroantimonate, bis(dodecylphenyl)iodonium-tetrafluoroborate, bis(dodecylphenyl)iodonium-tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium-hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium-hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium-tetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium-tetrakis(pentafluorophenyl)borate, etc.

[0163] In addition, commercially available products can also be used as the iodonium salt. Specifically, examples include "UV-9380C" (trade name) manufactured by GE Toshiba Silicone Co., Ltd., "RHODOSIL PHOTOINITIATOR 2074" (trade name) manufactured by RHODIA, "WPI-116" (trade name) and "WPI-113" (trade name) manufactured by Fujifilm Wako Pure Chemical Corporation, etc.

[0164] These can be used alone or in combination of two or more.

[0165] Examples of the sulfonium salt include bis[4-(diphenylsulfonium)phenyl]sulfide-bis(hexafluorophosphate), bis[4-(diphenylsulfonium)phenyl]sulfide-bis(hexafluoroantimonate), bis[4-(diphenylsulfonium)phenyl]sulfide-bis(tetrafluoroborate), bis[4-(diphenylsulfonium)phenyl]sulfide-tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium-hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium-hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium-tetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfonium-tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium-hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium-tetrakis(pentafluorophenyl)borate, bis[4-(bis(4-(2-hydroxyethoxy))phenylsulfonium)phenyl]sulfide-bis(hexafluorophosphate), bis[4-(bis(4-(2-hydroxyethoxy))phenylsulfonium)phenyl]sulfide-bis(hexafluoroantimonate), bis[4-(bis(4-(2-hydroxyethoxy))phenylsulfonium)phenyl]sulfide-bis(tetrafluoroborate), bis[4-(bis(4-(2-hydroxyethoxy))phenylsulfonium)phenyl]sulfide·tetrakis(pentafluorophenyl)borate, etc.

[0166] In addition, commercially available products can also be used as the sulfonium salt. Specifically, for example, "Cyracure UVI-6990" (trade name), "Cyracure UVI-6992" (trade name), and "Cyracure UVI-6974" manufactured by Dow Chemical Japan Co., Ltd., "Adeca Optomer SP-150" (trade name), "Adeca Optomer SP-152" (trade name), "Adeca Optomer SP-170" (trade name), and "Adeca Optomer SP-172" (trade name) manufactured by ADEKA Corporation, etc.

[0167] These can be used alone or in combination of two or more.

[0168] Examples of the diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate, etc. These can be used alone or in combination of two or more.

[0169] 3-4. Thermal cationic polymerization initiator

[0170] The thermal cationic polymerization initiator used in the present disclosure is not particularly limited, and examples thereof include sulfonium salts, phosphonium salts, and quaternary ammonium salts, etc. Among these, sulfonium salts are preferred.

[0171] Examples of the counter anion in the thermal cationic polymerization initiator include, for example, AsF6 - , SbF6 - , PF6 - , B(C6F5)4- etc.

[0172] Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, tris(4-methoxyphenyl)sulfonium hexafluoroarsenate, diphenyl(4-phenylthiophenyl)sulfonium hexafluoroarsenate, and the like.

[0173] In addition, commercially available products can also be used as the sulfonium salt. Specifically, for example, "ADEKA OPton CP-66" (trade name) and "ADEKA OPton CP-77" (trade name) manufactured by ADEKA Corporation, "San Aid SI-60L" (trade name), "San Aid SI-80L" (trade name), and "San Aid SI-100L" (trade name) manufactured by San Shin Chemical Industry Co., Ltd., and the like can be mentioned.

[0174] These can be used alone or in combination of two or more.

[0175] Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like.

[0176] Examples of the quaternary ammonium salt include N,N-dimethyl-N-benzylaniline hexafluoroantimonate, N,N-diethyl-N-benzylaniline tetrafluoroborate, N,N-dimethyl-N-benzylpyridine hexafluoroantimonate, N,N-diethyl-N-benzylpyridine trifluoromethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl)pyridine hexafluoroantimonate, N,N-diethyl-N-(4-methoxybenzyl)pyridine hexafluoroantimonate, N,N-diethyl-N-(4-methoxybenzyl)toluidine hexafluoroantimonate, N,N-dimethyl-N-(4-methoxybenzyl)toluidine hexafluoroantimonate, and the like.

[0177] These can be used alone or in combination of two or more.

[0178] 4. Undercoat agent composition for laminating inorganic substances

[0179] The undercoat agent composition for laminating inorganic substances of the present disclosure (hereinafter also referred to as "the composition of the present disclosure") contains the polysiloxane compound, free radical polymerization initiator, and / or cationic polymerization initiator related to the present disclosure.

[0180] The polysiloxane compound related to the present disclosure has excellent fluidity and curability, and as described later, has excellent adhesion to the inorganic substance layer laminated on the surface of the cured product by the dry film-forming method. In addition, the cured product has excellent heat resistance, scratch resistance, and / or hardness. Therefore, the composition of the present disclosure can be used as an undercoat agent coated on a resin substrate so that an inorganic substance layer can be laminated on the resin substrate by the dry film-forming method.

[0181] The composition of the present disclosure contains the polysiloxane compound and a radical polymerization initiator and / or a cationic polymerization initiator, and can be formulated with various components (hereinafter referred to as "other components") as needed.

[0182] As the other components, preferably polymerizable compounds that can be polymerized together with the polysiloxane compound, i.e., (meth)acrylate compounds, cationic polymerizable compounds, and compounds having an ethylenically unsaturated group, radical polymerization inhibitors, antioxidants, solvents, heat resistance improvers, and silicones, etc.

[0183] The other components will be described below.

[0184] 4-1. (Meth)acrylate compound

[0185] The composition of the present disclosure contains the polysiloxane compound represented by the formula (1). Further, for the purpose of adjusting physical properties such as scratch resistance and hardness of the cured product formed from the composition of the present disclosure, or adjusting the viscosity and curability of the composition of the present disclosure, etc., a compound having an acryloyl group or a methacryloyl group (hereinafter referred to as a "(meth)acrylate compound") can be formulated.

[0186] The (meth)acrylate compound is not particularly limited, and examples thereof include a compound having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylate"), and a compound having two or more (meth)acryloyl groups (hereinafter referred to as "polyfunctional (meth)acrylate").

[0187] As the monofunctional (meth)acrylate, examples include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate;

[0188] Monofunctional (meth)acrylates having an alicyclic group such as (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid tert-butylcyclohexyl ester, (meth)acrylic acid isobornyl ester, and (meth)acrylic acid tricyclodecane hydroxymethyl ester;

[0189] Monofunctional (meth)acrylates having an aromatic group such as benzyl (meth)acrylate and phenyl (meth)acrylate;

[0190] (Meth)acrylates of phenol ethylene oxide adducts, (meth)acrylates of phenol propylene oxide adducts, (meth)acrylates of modified nonylphenol ethylene oxide adducts, and (meth)acrylates of nonylphenol propylene oxide adducts, (meth)acrylates of alkylene oxide adducts of p-cumylphenol, (meth)acrylates of o-phenylphenol, and (meth)acrylates of alkylene oxide adducts of o-phenylphenol, etc., (meth)acrylates of alkylene oxide adducts of phenol derivatives;

[0191] Mono-functional (meth)acrylates having oxyalkyl groups such as 2-ethylhexyl carbitol (meth)acrylate;

[0192] Mono-functional (meth)acrylates having heterocycles such as tetrahydrofurfuryl (meth)acrylate and N-(2-(meth)acryloyloxyethyl)hexahydrophthalimide;

[0193] Hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyhexyl (meth)acrylate;

[0194] Mono-functional (meth)acrylates having a hydroxy group and an aromatic group such as 2-hydroxy-3-phenoxypropyl (meth)acrylate;

[0195] Alkylene glycol mono(meth)acrylates such as diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tripropylene glycol mono(meth)acrylate; and

[0196] Mono-functional (meth)acrylates having a carboxyl group such as ω-carboxy polycaprolactone mono(meth)acrylate and mono-hydroxyethyl phthalate (meth)acrylate, etc.

[0197] Examples of polyfunctional (meth)acrylates include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, di(meth)acrylate of ethylene oxide-modified neopentyl glycol, di(meth)acrylate of ethylene oxide-modified bisphenol A, di(meth)acrylate of propylene oxide-modified bisphenol A, di(meth)acrylate of ethylene oxide-modified hydrogenated bisphenol A, trimethylolpropane di(meth)acrylate, trimethylolpropane allyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate, and the like.

[0198] As the polyfunctional (meth)acrylate, a urethane (meth)acrylate can also be used.

[0199] Examples of the urethane (meth)acrylate include a compound obtained by an addition reaction of an organic polyisocyanate and a hydroxy group-containing (meth)acrylate, and a compound obtained by an addition reaction of an organic polyisocyanate, a polyol, and a hydroxy group-containing (meth)acrylate.

[0200] These can be used alone, or two or more of them can be used in combination, and different types of substances can also be used in combination.

[0201] Among them, examples of the polyol include low molecular weight polyols, polyether polyols, polyester polyols, polycarbonate polyols, and the like.

[0202] Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, and the like.

[0203] Examples of the polyether polyol include polypropylene glycol, polytetramethylene glycol, and the like.

[0204] Examples of the polyester polyol include reaction products of these low molecular weight polyols and / or polyether polyols with acid components such as dibasic acids or their acid anhydrides such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid.

[0205] These can be used alone, or two or more of them can be used in combination, and different types of substances can also be used in combination.

[0206] Examples of the organic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, etc.

[0207] Examples of the hydroxy group-containing (meth)acrylate include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, polyfunctional hydroxy group-containing (meth)acrylates such as trimethylolpropane tri(meth)acrylate, di(meth)acrylate of an adduct of 3 moles of alkylene oxide with isocyanuric acid, and dipentaerythritol pentaacrylate, etc. These can be used alone, or two or more of them can be used in combination, and different types of substances can also be used in combination.

[0208] When the (meth)acrylate compound is further contained in the composition of the present disclosure, its ratio is not particularly limited, but the ratio of the (meth)acrylate compound relative to 100 parts by weight of the polysiloxane compound represented by the formula (1) is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 20 parts by weight or less. From the viewpoint of the adhesion to the inorganic material layer, the lower the ratio of the (meth)acrylate compound is, the better, and the content is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

[0209] 4-2. Compound having an ethylenically unsaturated group other than the (meth)acrylate compound

[0210] For the purpose of reducing the viscosity when used without a solvent, improving the adhesion to the adherend, etc., a compound having one ethylenically unsaturated group in one molecule other than the above-mentioned (meth)acrylate compound can be added to the composition of the present disclosure.

[0211] As the ethylenically unsaturated group, (meth)acryloyl, maleimide group, (meth)acrylamide group, or vinyl is preferred.

[0212] Specific examples of the compound having the ethylenically unsaturated group include (meth)acrylic acid, Michael addition dimer of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acrylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam, etc.

[0213] These can be used alone, or two or more of them can be used in combination.

[0214] In addition, in the composition of the present disclosure, when a compound having the ethylenically unsaturated group is included, from the viewpoints of the adhesion and weather resistance of the inorganic material layer, the ratio of the compound having the ethylenically unsaturated group to the total weight of the polysiloxane compound represented by the formula (1) is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

[0215] 4-3. Cationically polymerizable compound

[0216] In order to improve the hardness of the cured product and the adhesion to the adherend, when the polysiloxane represented by the formula (1) is a polysiloxane having a monovalent organic group, the composition of the present disclosure preferably contains a cationic polymerizable compound other than this, and the monovalent organic group has an epoxy group or an oxetanyl group.

[0217] The cationic polymerizable compound is a compound having cationic polymerizability other than the polysiloxane compound represented by the formula (1), and examples thereof include an epoxy compound (a compound having an epoxy group), other compounds having an oxetanyl group (other compounds containing an oxetanyl group), a compound having a vinyl ether group (a vinyl ether compound), and the like. These compounds may be used alone or in combination of two or more.

[0218] When the polysiloxane compound represented by the formula (1) has at least an oxetanyl group, the epoxy compound has an effect of smoothly promoting the cationic polymerization of the oxetanyl group in the polysiloxane compound represented by the formula (1), and thus is particularly preferred.

[0219] Examples of the epoxy compound include a monofunctional epoxy compound and a polyfunctional epoxy compound.

[0220] Examples of the polyfunctional epoxy compound include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, (3,4-epoxycyclohexyl)methyl 3,4-epoxycyclohexanecarboxylate (e.g., “celloxide 2021P” (trade name) manufactured by Daicel Corporation), bis(3,4-epoxycyclohexyl)adipate, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S diglycidyl ether, bisphenol F type epoxy resin, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, a compound in which both ends of polybutadiene are glycidyl etherified, o-cresol novolak type epoxy resin, m-cresol novolak type epoxy resin, p-cresol novolak type epoxy resin, phenol novolak type epoxy resin, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, internal epoxide of polybutadiene, a compound in which a double bond in a styrene-butadiene copolymer such as “EPOFRIEND” (trade name) manufactured by Daicel Corporation is partially epoxidized, a compound in which a part of an isoprene polymer part in a block copolymer having an ethylene-butene copolymer part and an isoprene polymer part such as “L-207” (trade name) manufactured by KRATON Corporation is epoxidized, a compound having a structure in which a vinyl group is epoxidized in an open-ring polymer of 4-vinylcyclohexene oxide such as “EHPE3150” (trade name) manufactured by Daicel Corporation, a cage-like silsesquioxane having a glycidyl group such as “Q-4” in “Q8 series” manufactured by Mayaterials Corporation, an alicyclic cage-like silsesquioxane having an epoxy group such as “Q-5” in “Q8 series” manufactured by Mayaterials Corporation, a sesquioxane compound containing an epoxy group, and epoxidized vegetable oil, etc.

[0221] From the viewpoint of weather resistance, the composition of the present disclosure more preferably contains a polyfunctional epoxy compound.

[0222] Examples of the monofunctional epoxy compound include α-olefin epoxides such as 1,2-epoxyhexadecane, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, and glycidyl methacrylate.

[0223] Examples of the other compound containing an oxetanyl group include monofunctional oxetane compounds and polyfunctional oxetane compounds.

[0224] Examples of the polyfunctional oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (XDO), di[2-(3-oxetanyl)butyl] ether (DOX), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetane-3-yl)methoxy]benzene (CTOX), 4,4'-bis[(3-ethyloxetane-3-yl)methoxy]biphenyl (4,4'-BPOX), 2,2'-bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl (2,2'-BPOX), 3,3',5,5'-tetramethyl[4,4'-bis(3-ethyloxetane-3-yl)methoxy]biphenyl (TM-BPOX), 2,7-bis[(3-ethyloxetane-3-yl)methoxy]naphthalene (2,7-NpDOX), 1,6-bis[(3-ethyloxetane-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane (OFH-DOX), 3(4),8(9)-bis[(1-ethyl-3-oxetanyl)methoxymethyl]-tricyclo[5.2.1.02.6]decane, 1,2-bis[2-[(1-ethyl-3-oxetanyl)methoxy]ethylthio]ethane, 4,4'-bis[(1-ethyl-3-oxetanyl)methyl]thiodiphenyl sulfide, 2,3-bis[(3-ethyloxetane-3-yl)methoxymethyl]norbornane (NDMOX), 2-ethyl-2-[(3-ethyloxetane-3-yl)methoxymethyl]-1,3-O-bis[(1-ethyl-3-oxetanyl)methyl]-propane-1,3-diol (TMPTOX), 2,2-dimethyl-1,3-O-bis[(3-ethyloxetane-3-yl)methyl]-propane-1,3-diol (NPGOX), 2-butyl-2-ethyl-1,3-O-bis[(3-ethyloxetane-3-yl)methyl]-propane-1,3-diol, 1,4-O-bis[(3-ethyloxetane-3-yl)methyl]-butane-1,4-diol, 2,4,6-O-tris[(3-ethyloxetane-3-yl)methyl]cyanuric acid, the etherified product of bisphenol A and 3-ethyl-3-chloromethyloxetane (hereinafter referred to as "OXC") (BisAOX), the etherified product of bisphenol F and OXC (BisFOX), the etherified product of phenol novolac and OXC (PNOX), the etherified product of cresol novolac and OXC (CNOX), oxetanyl silsesquioxane (OX-SQ), and the silanolate of 3-ethyl-3-hydroxymethyloxetane (OX-SC), etc.

[0225] In addition, as the monofunctional oxetane compound, 3-ethyl-3-(2-ethylhexoxymethyl)oxetane (EHOX), 3-ethyl-3-(dodecyloxymethyl)oxetane (OXR-12), 3-ethyl-3-(octadecyloxymethyl)oxetane (OXR-18), 3-ethyl-3-(phenoxymethyl)oxetane (POX), 3-ethyl-3-hydroxymethyloxetane (OXA), etc. can be mentioned.

[0226] Among these, dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexyl)adipate, and a sesquioxane compound containing an epoxy group are preferred, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate and a sesquioxane compound containing the following epoxy group are more preferred. In addition, from the viewpoint of improving the adhesion of the inorganic material layer, an organic-inorganic hybrid compound having an epoxy group such as a sesquioxane compound containing an epoxy group and a silicone compound containing an epoxy group is particularly preferred.

[0227] [Chemical formula 11]

[0228]

[0229] As the vinyl ether compound, a monofunctional vinyl ether compound, a polyfunctional vinyl ether compound, etc. can be mentioned.

[0230] As the polyfunctional vinyl ether compound, cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, novolac type divinyl ether, etc. can be mentioned.

[0231] In addition, as the monofunctional vinyl ether compound, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, dodecene vinyl ether, propenyl ether propylene carbonate, cyclohexyl vinyl ether, etc. can be mentioned.

[0232] When the cation-curable composition of the present disclosure contains the cation-polymerizable compound, the content of the cation-polymerizable compound is not particularly limited, and is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and further preferably 1 to 25 parts by weight with respect to 100 parts by weight of the polysiloxane compound represented by the formula (1). When the content of the cation-polymerizable compound is within this range, the curability of the composition of the present disclosure and the hardness of the obtained cured product are excellent.

[0233] In addition, in the composition of the present disclosure, when a cationic polymerizable compound other than the polysiloxane compound represented by the formula (1) is included, from the viewpoint of the adhesion of the inorganic material layer, the content is preferably 25% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less, relative to the total amount of the polysiloxane compound represented by the formula (1).

[0234] 4-4. Organic polymer

[0235] For the purpose of reducing the curing shrinkage rate with inexpensive components, etc., an organic polymer can also be incorporated into the composition of the present disclosure.

[0236] Preferred polymers include (meth)acrylic polymers, and preferred constituent monomers include cyclohexyl methacrylate, (meth)acrylic cyclohexyl ester, N-(2-(meth)acryloyloxyethyl)tetrahydrophthalimide, etc.

[0237] In addition, when the organic polymer is included in the composition of the present disclosure, from the viewpoints of the adhesion to the inorganic material layer and weather resistance, the content is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less, relative to the total amount of the polysiloxane compound represented by the formula (1).

[0238] 4-5. Radical polymerization inhibitor and antioxidant

[0239] For the purpose of improving storage stability and thermal stability, a radical polymerization inhibitor and an antioxidant can be added to the composition of the present disclosure.

[0240] The polymerization inhibitor and antioxidant used are not particularly limited, and known radical scavengers can be used.

[0241] Specific examples of the radical polymerization inhibitor include phenolic compounds such as hydroquinone and hydroquinone monomethyl ether.

[0242] Specific examples of the antioxidant include hindered phenol antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, and pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), and 3-hydroxybenzenethiol, etc. In addition, α-nitroso-β-naphthol, p-benzoquinone, and copper salts, etc. can be mentioned. Furthermore, aluminum tris(N-nitroso-N-phenylhydroxylamine) of Fuji Film Wako Pure Chemical Industries, Ltd. and 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate of Sumitomo Chemical Co., Ltd. can also be used. These can be used alone or in combination of two or more.

[0243] In addition, sulfur-based secondary antioxidants such as 4,6-bis(octylthiomethyl)-O-cresol and phosphorus-based secondary antioxidants can be used in combination and added.

[0244] 4-6. Solvent

[0245] When the composition of the present disclosure is in a liquid state, it can be directly coated on the surface of the substrate, but it can also be diluted for use as needed. In the case of using a solvent, a solvent capable of dissolving the polysiloxane compound according to the present disclosure is preferred, and various organic solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellosolve solvents can be cited.

[0246] There is no particular limitation on the organic solvent, and examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, and isobutyl alcohol; alkyl glycol monoalkyl ethers such as propylene glycol monomethyl ether; aromatic compounds such as toluene and xylene; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dibutyl ether; and N-methylpyrrolidone. These can be used alone or in combination of two or more.

[0247] In the case of using a solvent, it is preferred to volatilize the solvent contained in the coated film before the composition of the present disclosure is cured. The volatilization of the solvent can be carried out in air or in an inert gas atmosphere. In order to volatilize the solvent, heating can be carried out, but the heating temperature at this time is preferably less than 100°C.

[0248] 4-7. Heat resistance improver

[0249] The composition of the present disclosure can contain a heat resistance improver.

[0250] There is no particular limitation on the heat resistance improver, and known heat resistance improvers can be used. Examples thereof include metal salts of organic carboxylic acids such as iron(III) tris(2-ethylhexanoate), cerium(III) tris(2-ethylhexanoate), zirconium(IV) tetrakis(2-ethylhexanoate), and zirconium(IV) bis(2-ethylhexanoate) oxide; and metal oxides such as iron oxide, cerium oxide, and zirconium oxide.

[0251] There is no particular limitation on the usage ratio of the heat resistance improver. Relative to 100 parts by weight of the total amount of the polysiloxane compound according to the present disclosure, it is, for example, 0 to 10,000 weight ppm, for example, 1 to 1,000 weight ppm, for example, 5 to 500 weight ppm, for example, 10 to 300 weight ppm.

[0252] By adding a heat resistance improver, it is possible to suppress the increase or decrease in the thermogravimetric reduction temperature, use it under heating and at room temperature, and suppress the decrease in relative permittivity, the decrease in insulation, the generation of cracks, and the coloring during storage, etc.

[0253] 4-8. Silicone

[0254] The composition of the present disclosure may contain silicone.

[0255] As the silicone, there is no particular limitation, and known silicones can be used. Examples include polydimethylsilicone, polydiphenylsilicone, polymethylphenylsilicone, etc., and functional groups may be present at its terminals and / or side chains. As the said functional groups, there is no particular limitation, and examples include (meth)acryloyl, epoxy group, oxetanyl, vinyl, hydroxyl group, carboxyl group, amino group, thiol group, etc.

[0256] The usage ratio of the silicone is not particularly limited. With respect to 100 parts by weight of the total amount of the polysiloxane compound related to the present disclosure, it is, for example, 0 to 100 parts by weight, for example, 1 to 50 parts by weight, for example, 5 to 40 parts by weight, for example, 5 to 30 parts by weight.

[0257] 4-9. Other components other than those described above

[0258] As other components of the composition of the present disclosure, components other than the said components can be blended as needed.

[0259] Specifically, it can contain any other auxiliary agents such as surfactants, antistatic agents (such as conductive polymers), leveling agents such as silicone polymers and fluorine atom-containing polymers, photosensitizers, ultraviolet absorbers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, nanoparticles, nanofibers, nanosheets, and various fillers such as silica and alumina. In addition, it can also contain silane reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.

[0260] 5. Resin substrate

[0261] The resin substrate for laminating the inorganic material layer involved in the present disclosure is not particularly limited, and examples thereof include polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin (PC), polyurethane resin, epoxy resin, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), polystyrene resin, polyvinyl chloride resin, polyacrylonitrile resin, polyimide resin, acrylic resins such as polyacrylate and polymethyl methacrylate (PMMA), cycloolefin polymer (COP), cycloolefin copolymer (COC), acetate resin, vinyl fluoride resin, polyarylate, cellophane, polyethersulfone, norbornene resin, and acetyl cellulose resins such as triacetyl cellulose (TAC), and various fiber-reinforced resin plastics (FRP), etc.

[0262] In addition, as the resin substrate, a resin substrate having appropriate and suitable physical properties is preferably used according to the intended use. For example, from the viewpoint of heat resistance, the melting point is preferably 150 °C or higher, more preferably 200 °C or higher. For example, from the viewpoint of optical properties, haze (blur), birefringence, refractive index, etc. can be cited. For example, the haze (ASTM D1003) is preferably 2% or less, more preferably 0.5% or less. For example, the retardation amount (parallel Nicol rotation method) is preferably 30 or less, more preferably 20 or less, and further preferably 5 or less. For example, the refractive index is preferably 1.48 or higher.

[0263] For example, from the viewpoint of optical properties, polycarbonate resin and polycyclohexyl methacrylate are preferable. From the viewpoint of gas barrier properties, polyethylene terephthalate is preferable.

[0264] Furthermore, as such a resin substrate, a resin substrate having excellent coatability with the undercoat agent composition of the present disclosure and adhesion to its cured product is preferably used. However, in order to further improve the adhesion of the cured product for laminating the inorganic material layer of the present disclosure, for example, a resin substrate subjected to surface activation treatments such as corona discharge treatment, ultraviolet irradiation treatment, and plasma treatment on the surface of the resin substrate can be used.

[0265] In addition, the shape of the resin substrate used in the present disclosure is not particularly limited, and for example, a film, sheet, lens, plate, etc. can be arbitrarily selected according to the use.

[0266] 6. Inorganic substance layer

[0267] As the inorganic material layer in the present disclosure, as long as it is formed by a dry film-forming method, there is no particular limitation, and examples thereof include layers mainly composed of various metals or metal oxides, nitrides, and sulfides having at least one or more elements such as Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B, Zr, Sn, Ta, Ag, and Pt.

[0268] As materials for forming the inorganic material layer, specifically, for example, as low refractive index materials, sodium fluoride, cryolite, johannsenite, lithium fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, strontium fluoride, zirconium fluoride, silicon dioxide, barium fluoride, yttrium fluoride, etc. can be cited; as medium refractive index materials, OL-B, lanthanum fluoride, neodymium fluoride, gadolinium fluoride, cerium fluoride, aluminum oxide, tungsten oxide, magnesium oxide, lead fluoride, silicon monoxide, lanthanum oxide, yttrium oxide, scandium oxide, europium oxide, molybdenum oxide, samarium fluoride, praseodymium oxide, etc. can be cited; as high refractive index materials, indium oxide, tin oxide, hafnium oxide, tantalum oxide, zirconium oxide, antimony oxide, zinc oxide, cerium oxide, OS-5, neodymium oxide, niobium oxide, zinc sulfide, titanium trioxide, titanium pentoxide, titanium monoxide, titanium dioxide, silicon, germanium, etc. can be cited; as metals, silver, aluminum, gold, chromium, copper, hafnium, indium, molybdenum, nickel, platinum, tantalum, titanium, tungsten, etc. can be cited; and further, as other functional agents, germanium oxide, ITO, MS-DC100, MS-SY, etc. can be cited.

[0269] In addition, for example, a diamond-like carbon (hereinafter referred to as DLC) film layer having high hardness and excellent insulating properties can also be cited. The DLC film is an amorphous carbon film mainly composed of sp 3 bonds between carbons, and is a diamond-like carbon film that is very hard, has a low coefficient of friction, abrasion resistance, corrosion resistance, gas barrier properties, and excellent insulating properties.

[0270] The inorganic material layer in the present disclosure can be a multilayer as long as there is at least one layer or more. When the inorganic material layer is a multilayer, its stacking order and the type of the inorganic material layer are not particularly limited. In addition, as the inorganic material layer, it can also be various functional layers such as an ultraviolet absorption layer and a functional layer.

[0271] When one layer of the inorganic material layer is a DLC layer, from the viewpoint of having the above-mentioned properties, it is preferably stacked as the outermost layer on the basis of stacking the metal oxide layer.

[0272] These inorganic material layers can be arbitrarily selected according to the use.

[0273] The method for laminating the inorganic material layer in the present disclosure is not particularly limited as long as it is a dry film-forming method. Examples thereof include vacuum evaporation such as resistance heating evaporation, electron beam heating evaporation, and high-frequency induction heating evaporation, molecular beam epitaxy, ion beam deposition, ion plating, sputtering, laser ablation, and other physical vapor deposition methods (hereinafter also referred to as "PVD" or physical evaporation method), or chemical vapor deposition methods such as thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, catCVD, and metalorganic CVD (hereinafter also referred to as "CVD" or chemical evaporation method). However, a physical evaporation method is preferred.

[0274] The dry film-forming method mentioned here refers to a method of treating the material surface by using a gas phase or dissolved state, and is generally also called a dry process.

[0275] The thickness of the inorganic material layer is not particularly limited and can be arbitrarily set according to the purpose and use. However, for example, from the viewpoint of the scratch resistance of the inorganic material layer, it is preferably 5 nm or more, more preferably 50 nm or more, further preferably 100 nm or more, and still further preferably 150 nm or more. The upper limit of the thickness of the inorganic material layer is not particularly limited, and is preferably 25 μm or less, more preferably 15 μm or less, and further preferably 10 μm or less. In order to adjust the thickness of the inorganic material layer, in physical evaporation, the treatment time and the like can be adjusted.

[0276] In the laminate according to the present disclosure, the inorganic material layer laminated as described above is an inorganic substance, and thus has excellent appearance, weather resistance, and scratch resistance that an organic film does not have. In addition, the adhesion to the cured product for laminating the inorganic material layer can be made excellent, and the weather resistance, water resistance, and scratch resistance are very excellent.

[0277] 8. Method for producing an undercoat agent composition for laminating inorganic substances and a cured product thereof

[0278] The curable composition of the present disclosure can be obtained by mixing raw material components. When mixing, a known mixer or the like can be used. Specifically, a reaction flask, a tank-changing mixer, a planetary mixer, a disperser, a Henschel mixer, a kneader, an ink roller, an extruder, a three-roll mill, a sand mill, etc. can be cited.

[0279] After coating the suitable resin substrate with the composition of the present disclosure and the like, the reaction of the polymerizable group is usually carried out and cured by a method of irradiating active energy rays, a heating method, a method of using both active energy ray irradiation and heating, etc.

[0280] The composition of the present disclosure may or may not contain a solvent. In the case of containing a solvent, it is usually supplied for curing after removing the solvent as described above.

[0281] 8-1. Curable composition

[0282] The composition of the present disclosure comprises the polysiloxane compound represented by the formula (1), and the radical polymerization initiator and / or cationic polymerization initiator. Further, the other components may be included. When a solvent is included as the other component, generally, before the composition of the present disclosure is cured, the solvent is removed by drying or the like to obtain a cured product, which is used as a primer coat. Therefore, among all the components other than the solvent in the composition of the present disclosure, the proportion of the polysiloxane compound represented by the formula (1) is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, and still more preferably 90 parts by weight or more. By setting it within the preferred range, a cured product with good adhesion to the inorganic material layer can be obtained.

[0283] In the case of a mixed solvent, its usage amount can be arbitrarily set according to the purpose and is not particularly limited. For example, relative to 100 parts by weight of the polysiloxane compound represented by the formula (1), it can be 1 to 20,000 parts by weight, more preferably 10 to 1,000 parts by weight, and still more preferably 50 to 500 parts by weight.

[0284] 8-2. Coating method

[0285] The method for coating the composition of the present disclosure on a resin substrate is not particularly limited and is appropriately selected according to the constituent material and shape of the substrate, etc. For example, common coating methods such as casting method, spin coating method, bar coating method, dip coating method, spraying method, roll coating method, flow coating method, and gravure coating method can be used.

[0286] The coating thickness of the composition of the present disclosure is not particularly limited and can be arbitrarily set according to the purpose. It is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and still more preferably 1 to 10 μm.

[0287] 8-3. Curing method

[0288] In the present disclosure, according to whether the curable composition is curable by active energy rays and / or heat, its curing method and curing conditions are selected. In addition, the curing conditions are appropriately selected according to the type and amount of the polymerization initiator and the types of other polymerizable compounds contained in the composition of the present disclosure (in the case of curing by active energy rays, for example, the type of light source and the light irradiation amount, etc.; in the case of heat curing, the heating temperature and heating time, etc.).

[0289] (1) Actinic energy ray curing method

[0290] When the composition of the present disclosure is a curable composition for active energy rays, as its curing method, irradiation with active energy rays can be performed using a known active energy ray irradiation device or the like. Examples of the active energy rays include electron beams, and light such as ultraviolet rays, visible rays, and X-rays. However, light is preferably used because a cheap device can be used, and ultraviolet rays are more preferably used.

[0291] Examples of the ultraviolet irradiation device include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, a chemical lamp, a black light, a microwave-excited mercury lamp, and a light-emitting diode (LED).

[0292] The light irradiation intensity on the film coated with the composition of the present disclosure can be selected according to the purpose, use, etc. The light irradiation intensity in the light wavelength region effective for activating the active energy ray polymerization initiator (referred to as a photoinitiator in the case of photocuring) (varies depending on the type of the photoinitiator, but light with a wavelength of 220 to 460 nm is preferably used) is preferably 0.1 to 1000 mW / cm 2 .

[0293] In addition, the irradiation energy should be appropriately set according to the type of the active energy ray and the composition, and the light irradiation time on the film can also be selected according to the purpose, use, etc. It is preferable to set the cumulative light amount, which is the product of the light irradiation intensity and the light irradiation time in the light wavelength region, to 10 to 7,000 mJ / cm 2 . More preferably, it is 200 to 5,000 mJ / cm 2 , and further preferably 500 to 3500 mJ / cm 2 . As long as the cumulative light amount is within the above range, the curing of the composition can be smoothly performed, and a uniform cured product can be easily obtained.

[0294] In addition, heat curing can be appropriately combined before and / or after photocuring.

[0295] For example, two-stage curing can be performed. In this case, when the composition of the present disclosure penetrates into a substrate having a portion that becomes a shadow when irradiated with light, and then light is irradiated, first, the composition of the present disclosure at the portion irradiated with light is cured, and then heat is applied to cure the composition of the present disclosure at the portion not irradiated with light. Such a substrate is not particularly limited, and examples thereof include substrates having complex shapes such as cloth-like, fibrous, powdery, porous, and uneven shapes, and may also be a combination of two or more of these shapes.

[0296] (2) Thermal curing method

[0297] When the composition of the present disclosure is a thermosetting composition, its curing method and curing conditions are not particularly limited.

[0298] The curing temperature is preferably 80°C to 200°C, more preferably 100°C to 180°C, and further preferably 110°C to 150°C. Additionally, the curing temperature can be a constant temperature or a temperature increase. Furthermore, a temperature increase and a temperature decrease can also be combined.

[0299] The curing time is appropriately selected according to the type of the thermal polymerization initiator and the content ratio of other components, etc., and is preferably 10 to 360 minutes, more preferably 30 to 300 minutes, and further preferably 60 to 240 minutes. By curing the film under the above preferred conditions, a uniform cured film without swelling, cracks, etc. can be formed.

[0300] 8-4. Physical properties of cured product

[0301] The cured product obtained by curing the composition of the present disclosure (also simply referred to as "the cured product of the present disclosure" in this specification) has excellent adhesion to the resin substrate and to the inorganic material layer. The index of adhesion is not particularly limited, and known indexes are applicable, but for example, evaluation indexes based on a checkerboard peel test (cross-cut method) etc. can be cited. In the case of adopting the checkerboard peel test, for the inorganic material layer of the laminate, its adhesion can be evaluated according to JIS K5600-5-6 (ISO-2409).

[0302] In addition, the cured product of the present disclosure has excellent hardness. The index of hardness is not particularly limited, and known indexes are applicable, but for example, evaluation indexes based on a pencil hardness test and an abrasion resistance test (scratch test) etc. can be cited.

[0303] In addition, the cured product of the present disclosure is excellent in transparency, coloring resistance, ultraviolet resistance, flexibility, resin substrate followability, weather resistance, chemical resistance, abrasion resistance, durability, heat resistance, etc.

[0304] The cured product of the present disclosure is obtained by curing a composition mainly composed of the polysiloxane compound represented by the formula (1). The polysiloxane compound related to the present disclosure contains T units, and preferably also contains D units and / or M units. Therefore, the SiO content rate in the cured product, that is, the content rate of the inorganic components contained in the cured product, is high, and thus the adhesion to the inorganic material layer laminated thereon is excellent. The cured product of the present disclosure containing D units and / or M units is more excellent in flexibility or resin substrate followability, and thus is preferred. In addition, the cured product of the present disclosure containing D units and / or M units is more excellent in surface smoothness, and thus is preferred.

[0305] By appropriately balancing and adjusting the composition ratios of the respective components of the polysiloxane according to the purpose and use, particularly the composition ratios of the structural unit (b) and the structural unit (c), the cured product of the polysiloxane compound according to the present disclosure can exhibit physical properties such as good adhesion to the resin substrate, good adhesion to the inorganic material layer, hardness, flexibility, and resin substrate followability in good balance.

[0306] 9. Laminate

[0307] The laminate of the present disclosure includes the above-mentioned cured product of the present disclosure, a resin substrate, and an inorganic material layer. The laminate of the present disclosure preferably includes: at least one of the resin substrates, a cured product for laminating the inorganic material layer of the present disclosure on which the inorganic material layer of the present disclosure laminated thereon is cured, and further at least one of the inorganic material layers laminated thereon. Its structure is not particularly limited and can be arbitrarily selected according to the purpose, use, etc. For example, when the resin substrate is a film, the cured product of the present disclosure and the inorganic material layer can be laminated in sequence on one surface, and in addition, the cured product of the present disclosure and the inorganic material layer can be laminated in sequence on the two surfaces of the film, respectively.

[0308] 10. Use

[0309] As the use of the laminate of the present disclosure, there is no particular limitation, and examples include the outer panel part of automobile bodies such as passenger cars, trucks, motorcycles, and buses; automobile parts; the outer panel part of household electrical appliance products such as mobile phones and audio equipment, etc., among which, the outer panel part of automobile bodies and automobile parts are preferred.

[0310] In addition, it can be used for packaging materials for parts or components requiring moisture resistance in various devices such as optical elements, liquid crystal displays or organic EL displays, semiconductor devices, thin film solar cells, etc., and packaging of foods, clothes, electronic components, etc.

[0311] In addition, it can be used as a decorative printed film laminate, which is useful as a decorative film for display substrates, touch panels, thin films with transparent strip electrodes, lens sheets, optical waveguides, solar cell substrates, optical discs, various transparent substrates, etc.

[0312] The functions of having an inorganic material layer or a laminate are not particularly limited, and examples include antireflection, antifogging, gas barrier, hard coating, scratch resistance, wear resistance, appearance design, antistatic, conductive, moisture resistance, weather resistance, light resistance, waterproof, oil resistance, stain resistance, antibacterial, antiviral, anti-bioactivity, ultraviolet resistance, cosmic ray resistance, acid plasma resistance, atomic oxygen resistance, etc.

[0313] Examples

[0314] Next, the present disclosure will be specifically described based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0315] It should be noted that the weight-average molecular weight (hereinafter also referred to as Mw.) is separated by gel permeation chromatography (hereinafter referred to as "GPC.") in an isopropyl alcohol solvent at 40 °C using connected GPC columns "TSK gel G4000HX" and "TSK gel G2000HX" (manufactured by Tosoh Corporation), and calculated from the retention time using standard polystyrene.

[0316] In addition, the molar ratio of each structural unit of the obtained polysiloxane compound is determined by dissolving the sample in deuterated chloroform and performing 1 1H-NMR analysis, and if necessary, 29 Si-NMR analysis. The alkoxysilane monomer undergoes a quantitative reaction and is introduced into the polysiloxane compound, but the introduction rate of the M unit derived from the disiloxane monomer is not quantitatively introduced according to the composition of the polysiloxane compound.

[0317] The viscosity was measured at 25 °C using TVE22H manufactured by Toki Sangyo Co., Ltd. with a cone plate.

[0318] 〔Synthesis of Polysiloxane Compound〕

[0319] <Synthesis Example 1>

[0320] Using (3-acryloxypropyl)trimethoxysilane as the T monomer, which is a raw material silane monomer, isopropyl alcohol as the reaction solvent, and hydrochloric acid as the catalyst, hydrolysis and polycondensation reactions are carried out according to a known method, and then the solvent and the like are removed to obtain Polysiloxane Compound 1, which is a colorless transparent liquid. The results of the composition ratio, Mw, and viscosity (25 °C) of Polysiloxane Compound 1 are shown in Table 1.

[0321] <Synthesis Example 2>

[0322] Using (3-acryloxypropyl)trimethoxysilane as the T monomer and silanol-terminated polydimethylsiloxane as the D monomer, which are raw material silane monomers, isopropyl alcohol as the reaction solvent, and tetramethylammonium hydroxide as the catalyst, hydrolysis and polycondensation reactions are carried out according to a known method, and then the solvent and the like are removed to obtain Polysiloxane Compound 2, which is a colorless transparent liquid. The results of the composition ratio, Mw, and viscosity (25 °C) of Polysiloxane Compound 2 are shown in Table 1.

[0323] <Synthesis Examples 3 to 7>

[0324] Using T monomer, i.e., (3-acryloyloxypropyl)trimethoxysilane, and D monomer, i.e., dimethoxydimethylsilane, as raw material silane monomers, isopropyl alcohol as the reaction solvent, and hydrochloric acid as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the solvent and the like are removed to obtain polyorganosiloxane compounds 3 to 7, which are colorless transparent liquids. The molar ratio of each structural unit of the produced polyorganosiloxane compounds is the same as the feeding ratio of the raw material monomers. The results of the composition ratio, Mw, and viscosity (25 °C) of each polyorganosiloxane compound are shown in Table 1.

[0325] <Synthesis Example 8>

[0326] Using T monomer, i.e., (3-acryloyloxypropyl)trimethoxysilane, and M monomer, i.e., 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, as raw material silane monomers, isopropyl alcohol as the reaction solvent, and hydrochloric acid as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the solvent and the like are removed to obtain polyorganosiloxane compound 8, which is a colorless transparent liquid. 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane undergoes a quantitative reaction and is introduced into polyorganosiloxane compound 8. The results of the composition ratio, Mw, and viscosity (25 °C) of polyorganosiloxane compound 8 are shown in Table 1.

[0327] <Synthesis Example 9>

[0328] Using T monomer, i.e., (3-methacryloyloxypropyl)trimethoxysilane, as the raw material silane monomer, isopropyl alcohol as the reaction solvent, and hydrochloric acid as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the solvent and the like are removed to obtain polyorganosiloxane compound 9, which is a colorless transparent liquid. The results of the composition ratio, Mw, and viscosity (25 °C) of polyorganosiloxane compound 9 are shown in Table 1.

[0329] <Synthesis Example 10>

[0330] Using T monomer, i.e., (3-methacryloyloxypropyl)trimethoxysilane, and D monomer, i.e., dihydroxydimethylsiloxane-terminated polydimethylsiloxane, as raw material silane monomers, isopropyl alcohol as the reaction solvent, and tetramethylammonium hydroxide as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the solvent and the like are removed to obtain polyorganosiloxane compound 10, which is a colorless transparent liquid. The results of the composition ratio, Mw, and viscosity (25 °C) of polyorganosiloxane compound 10 are shown in Table 1.

[0331] <Synthesis Example 11>

[0332] Using T monomer, i.e., (3-methacryloxypropyl)trimethoxysilane, and D monomer, i.e., dimethoxydimethylsilane, as raw material silane monomers respectively, using isopropyl alcohol as the reaction solvent, and using hydrochloric acid as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the solvent etc. were removed to obtain polysiloxane compound 11, which is a colorless transparent liquid. The results of the composition ratio, Mw and viscosity (25 °C) of polysiloxane compound 11 are shown in Table 1.

[0333] <Synthesis Example 12>

[0334] Using 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane, i.e., T monomer, as the raw material silane monomer respectively, using isopropyl alcohol as the reaction solvent, and using tetramethylammonium hydroxide as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the solvent etc. were removed to obtain polysiloxane compound 12, which is a colorless transparent liquid. The results of the composition ratio, Mw and viscosity (25 °C) of polysiloxane compound 12 are shown in Table 1.

[0335] <Synthesis Example 13>

[0336] Using 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane, i.e., T monomer, and silanol-terminated polydimethylsiloxane, i.e., D monomer, as the raw material silane monomers respectively, using isopropyl alcohol as the reaction solvent, and using tetramethylammonium hydroxide as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the solvent etc. were removed to obtain polysiloxane compound 13, which is a colorless transparent liquid. The results of the composition ratio, Mw and viscosity (25 °C) of polysiloxane compound 13 are shown in Table 1.

[0337] <Synthesis Example 14>

[0338] Using tetramethoxysilane, i.e., Q monomer, and (3-methacryloxypropyl)trimethoxysilane, i.e., T monomer, as the raw material silane monomers respectively, using 1-propanol as the reaction solvent, and using tetramethylammonium hydroxide as the catalyst, after carrying out hydrolysis and polycondensation reactions according to a well-known method, the reaction solution was neutralized, the product was separated and extracted, and the solvent etc. were removed to obtain polysiloxane compound 14, which is a colorless solid. The results of the composition ratio and Mw of polysiloxane compound 14 are shown in Table 1. It should be noted that since it is a solid, viscosity measurement was not carried out.

[0339] The compositions of the polysiloxane compounds obtained in Synthesis Examples 1 to 14, the molar ratios of the respective structural units, Mw and viscosity (25 °C) are summarized in Table 1.

[0340] (Table 1)

[0341]

[0342] AC: 3-acryloxypropyl

[0343] MAC: 3-methacryloxypropyl

[0344] OX: 3-[(3-ethyloxetane-3-yl)methoxy]propyl

[0345] Me: methyl

[0346] Vi: vinyl

[0347] <Reference Example 1>

[0348] aronix M-405 (dipentaerythritol penta- and hexaacrylate) manufactured by Toagosei Co., Ltd. was directly used.

[0349] <Example 1>

[0350] (1) Preparation of photocurable undercoat agent composition

[0351] 10 g of the polysiloxane compound 1 obtained in Synthesis Example 1, 0.3 g of a photo radical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone (Omnirad 184 manufactured by IGM RESINS B.V., hereinafter also referred to as Om184), and 10 g of a solvent, propylene glycol monobutyl ether acetate (hereinafter also referred to as PGB) were respectively weighed into a 50 mL glass vial, and dissolved by stirring with a rotation-revolution mixer to prepare a photocurable undercoat agent composition.

[0352] (2) Coating on resin substrate and photocuring

[0353] The photocurable composition prepared in (1) above was coated on a plate made of polycarbonate (hereinafter also referred to as PC) (iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Company, Inc., thickness 1 mm) as a resin substrate using a bar coater, and after forming a film about 5 μm thick, it was heated at 65 °C for 5 minutes to dry the solvent. Then, ultraviolet irradiation was performed under the following conditions to produce a cured product.

[0354] [Ultraviolet irradiation conditions]

[0355] Lamp: 80 W / cm high-pressure mercury lamp

[0356] Lamp height: 10 cm

[0357] Conveyor belt speed: 5.7 m / min

[0358] Light irradiation intensity: 700 mW / cm 2

[0359] Accumulated light amount per pass: 360 mJ / cm 2

[0360] Atmosphere: In the atmosphere

[0361] Number of sweeps: 9 times

[0362] (3) Lamination of inorganic substance layer

[0363] On the photocured product produced in the above (2), platinum was laminated by sputtering under the following apparatus and conditions. The thickness of the platinum layer was about 10 nm.

[0364] [Platinum sputtering conditions]

[0365] Vacuum Equipment Manufacturing Co., Ltd. MSP-1S Magnetron Sputter Discharge Current: 30 mA, Process Time: 20 sec.

[0366] (4) Adhesion test of inorganic substance layer: Adhesion (cross-cut method)

[0367] For the inorganic material layer of the laminate produced through the above (1) to (3), the adhesion was evaluated according to JIS K5600-5-6 (ISO-2409). In 25 squares, the evaluation was carried out based on the number of peeled squares. The fewer the number of peeled squares, the higher the adhesion. In Example 1, the number of peeled squares was two.

[0368] It should be noted that in this evaluation, there were no peeled squares between the resin substrate and the photocured product of the undercoat agent composition.

[0369] The results of this example are summarized in Table 2.

[0370] <Example 2>

[0371] Except that a plate (Acrylite L manufactured by Mitsubishi Chemical Corporation, thickness 1 mm) made of polycyclohexyl methacrylate (hereinafter also referred to as PMMA) was used instead of polycarbonate as the resin substrate, a laminate was produced in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0372] <Example 3>

[0373] Except that SiO2 was laminated by ion plating instead of platinum as the inorganic material layer, a laminate was produced in the same manner as in Example 1, and the adhesion of the inorganic material layer was evaluated. The thickness of the SiO2 layer was about 200 nm. The results are shown in Table 2.

[0374] <Example 4>

[0375] A laminate was produced in the same manner as in Example 1 except that ZrO2 was laminated by ion plating instead of platinum as the inorganic layer, and the adhesion of the inorganic layer was evaluated. The thickness of the ZrO2 layer was about 200 nm. The results are shown in Table 2.

[0376] <Example 5>

[0377] A laminate was produced in the same manner as in Example 1 except that the polysiloxane compound 2 obtained in Synthesis Example 2 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0378] <Example 6>

[0379] A laminate was produced in the same manner as in Example 4 except that the polysiloxane compound 2 obtained in Synthesis Example 2 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0380] <Example 7>

[0381] A laminate was produced in the same manner as in Example 3 except that the polysiloxane compound 2 obtained in Synthesis Example 2 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0382] <Example 8>

[0383] A laminate was produced in the same manner as in Example 1 except that the polysiloxane compound 3 obtained in Synthesis Example 3 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0384] <Example 9>

[0385] A laminate was produced in the same manner as in Example 1 except that the polysiloxane compound 4 obtained in Synthesis Example 4 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0386] <Example 10>

[0387] A laminate was produced in the same manner as in Example 1 except that the polysiloxane compound 5 obtained in Synthesis Example 5 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0388] <Example 11>

[0389] A laminate was produced in the same manner as in Example 10, except that a plate (manufactured by Takiron-ci Co., Ltd., thickness 1 mm) made of polyethylene terephthalate (hereinafter also referred to as PET) was used instead of polycarbonate as the resin substrate, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0390] <Example 12>

[0391] A laminate was produced in the same manner as in Example 10, except that a plate (manufactured by TP Giken Co., Ltd., thickness 1 mm) made of 6 nylon (hereinafter also referred to as Nylon6) was used instead of polycarbonate as the resin substrate, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0392] <Example 13>

[0393] A laminate was produced in the same manner as in Example 3, except that the polysiloxane compound 5 obtained in Synthesis Example 5 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0394] <Example 14>

[0395] A laminate was produced in the same manner as in Example 4, except that the polysiloxane compound 5 obtained in Synthesis Example 5 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0396] <Example 15>

[0397] A laminate was produced in the same manner as in Example 1, except that the polysiloxane compound 6 obtained in Synthesis Example 6 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0398] <Example 16>

[0399] A laminate was produced in the same manner as in Example 1, except that the polysiloxane compound 7 obtained in Synthesis Example 7 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0400] <Example 17>

[0401] A laminate was produced in the same manner as in Example 1, except that the polysiloxane compound 8 obtained in Synthesis Example 8 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0402] <Example 18>

[0403] A laminate was produced in the same manner as in Example 1, except that the polysiloxane compound 9 obtained in Synthesis Example 9 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0404] <Example 19>

[0405] A laminate was produced in the same manner as in Example 18, except that polycyclohexyl methacrylate was used instead of polycarbonate as the resin substrate, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0406] <Example 20>

[0407] A laminate was produced in the same manner as in Example 4, except that the polysiloxane compound 9 obtained in Synthesis Example 9 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0408] <Example 21>

[0409] A laminate was produced in the same manner as in Example 1, except that the polysiloxane compound 10 obtained in Synthesis Example 10 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0410] <Example 22>

[0411] A laminate was produced in the same manner as in Example 3, except that the polysiloxane compound 10 obtained in Synthesis Example 10 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0412] <Example 23>

[0413] A laminate was produced in the same manner as in Example 4, except that the polysiloxane compound 10 obtained in Synthesis Example 10 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0414] <Example 24>

[0415] A laminate was produced in the same manner as in Example 1, except that the polysiloxane compound 11 obtained in Synthesis Example 11 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0416] <Example 25>

[0417] A laminate was produced in the same manner as in Example 24 except that polyethylene terephthalate was used instead of polycarbonate as the resin substrate, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0418] <Example 26>

[0419] A laminate was produced in the same manner as in Example 24 except that 6 nylon was used instead of polycarbonate as the resin substrate, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0420] <Example 27>

[0421] A laminate was produced in the same manner as in Example 3 except that the polysiloxane compound 11 obtained in Synthesis Example 11 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0422] <Example 28>

[0423] A laminate was produced in the same manner as in Example 4 except that the polysiloxane compound 11 obtained in Synthesis Example 11 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0424] <Example 29>

[0425] 9 g of the polysiloxane compound 12 obtained in Synthesis Example 12, 1 g of Daicel celloxide 2021P (3’,4’-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, hereinafter also referred to as CEL2021P), 0.2 g of a photo cationic polymerization initiator, PHOTO INITIATOR 2074 (manufactured by Solvay Japan Co., Ltd., hereinafter also referred to as PI2074), and 10 g of a solvent, PGB, were weighed into a 50 mL glass vial and dissolved by stirring with a rotation-revolution mixer to prepare a photocurable undercoat agent composition.

[0426] Using this composition, a laminate was produced in the same manner as in (2) to (4) of Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0427] <Example 30>

[0428] A laminate was produced in the same manner as in Example 29 except that the polysiloxane compound 13 obtained in Synthesis Example 13 was used instead of the polysiloxane compound 12 obtained in Synthesis Example 12, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0429] <Example 31>

[0430] A laminate was produced in the same manner as in Example 3, except that the polysiloxane compound 9 obtained in Synthesis Example 9 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0431] <Example 32>

[0432] A laminate was produced in the same manner as in Example 29, except that SiO2 was laminated by ion plating instead of platinum as the inorganic substance layer, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0433] <Example 33>

[0434] A laminate was produced in the same manner as in Example 3, except that the polysiloxane compound 14 obtained in Synthesis Example 14 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic substance layer was evaluated. The results are shown in Table 2.

[0435] <Example 34>

[0436] (1) Preparation of thermosetting undercoat agent composition

[0437] 10 g of the polysiloxane compound 11 obtained in Synthesis Example 11, 0.1 g of a thermal free radical polymerization initiator, tert-butyl peroxy(2-ethylhexanoate) (manufactured by NOF Corporation, perbutyl O, hereinafter also referred to as PBO), and 10 g of a solvent, PGB, were weighed into a 50 mL glass vial and stirred and dissolved using a rotation-revolution mixer to prepare a thermosetting undercoat agent composition.

[0438] (2) Coating on resin substrate and thermal curing

[0439] The thermosetting composition prepared in (1) above was coated on a plate made of polycarbonate (hereinafter also referred to as PC) (manufactured by Mitsubishi Gas Chemical Company, Inc., iupilon NF-2000, thickness 1 mm) as a resin substrate using a bar coater, and after forming a film about 5 μm thick, the solvent was dried by heating at 65 °C for 5 minutes. Then, in a thermostat, it was heated at 120 °C for 1 hour to produce a cured product.

[0440] (3) Lamination of inorganic substance layer

[0441] ZrO2 was laminated on the thermoset produced in (2) above by ion plating.

[0442] (4) Adhesion test of inorganic substance layer: Adhesion (cross-cut method)

[0443] For the inorganic layer of the laminate produced by the above (1) to (3), the adhesion was evaluated according to JIS K5600-5-6 (ISO-2409). In the 25-square grid, the evaluation was made based on the number of peeled squares. The fewer the number of peeled squares, the higher the adhesion. In Example 34, there were no peeled squares, that is, 0 squares.

[0444] It should be noted that in this evaluation, there were no peeled squares between the resin substrate and the thermoset of the undercoat agent composition.

[0445] The results of this example are summarized in Table 2.

[0446] <Example 35>

[0447] 9 g of the polysiloxane compound 13 obtained in Synthesis Example 13, 1 g of CEL2021P, 0.1 g of the thermal cationic polymerization initiator San Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd., hereinafter also referred to as SI100L), and 10 g of the solvent PGB were weighed into a 50 mL glass vial and dissolved by stirring with a rotation-revolution mixer to prepare a thermosetting undercoat agent composition.

[0448] Except for using this composition and having the inorganic layer as SiO2, a laminate was produced in the same manner as in (2) to (4) of Example 34, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0449] <Comparative Example 1>

[0450] Except for using M-405 described in Reference Example 1 to replace the polysiloxane compound 1 obtained in Synthesis Example 1, a laminate was produced in the same manner as in Example 1, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0451] <Comparative Examples 2 to 4>

[0452] Except for using polycyclohexyl methacrylate, polyethylene terephthalate, or 6 nylon to replace polycarbonate as the resin substrate, a laminate was produced in the same manner as in Comparative Example 1, and the adhesion of each inorganic layer was evaluated. The results are shown in Table 2.

[0453] <Comparative Example 5>

[0454] Except for using M-405 described in Reference Example 1 to replace the polysiloxane compound 1 obtained in Synthesis Example 1, a laminate was produced in the same manner as in Example 3, and the adhesion of the inorganic layer was evaluated. The results are shown in Table 2.

[0455] <Comparative Example 6>

[0456] A laminate was produced in the same manner as in Example 4, except that M-405 described in Reference Example 1 was used instead of the polysiloxane compound 1 obtained in Synthesis Example 1, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0457] <Comparative Examples 7 to 10>

[0458] A laminate was produced in the same manner as in Example 1, except that polycarbonate, polycyclohexyl methacrylate, polyethylene terephthalate, or 6-nylon was used as the resin substrate and no undercoat layer for inorganic material lamination was provided, and the adhesion of each inorganic material layer was evaluated. The results are shown in Table 2.

[0459] <Comparative Example 11>

[0460] A laminate was produced in the same manner as in Example 3, except that no undercoat layer for inorganic material lamination was provided, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0461] <Comparative Example 12>

[0462] A laminate was produced in the same manner as in Example 4, except that no undercoat layer for inorganic material lamination was provided, and the adhesion of the inorganic material layer was evaluated. The results are shown in Table 2.

[0463] (5) Adhesion test of inorganic substance layer after hot water treatment: Adhesion (cross-cut method)

[0464] <Examples 36 to 41>

[0465] The laminates produced in the manner of Example 3, Example 31, Example 22, Example 27, Example 32, and Example 33 were immersed in warm water at 90 °C for two hours and then dried at room temperature for 17 hours (hereinafter, also referred to as "after warm water treatment"). Then, the adhesion of each inorganic material layer was evaluated in the same manner as in Example 1(4). The results are shown in Table 3.

[0466] <Comparative Examples 13 and 14>

[0467] The laminates produced in the manner of Comparative Example 5 and Comparative Example 11 were immersed in warm water at 90 °C for two hours and then dried at room temperature for 17 hours. Then, the adhesion of each inorganic material layer was evaluated in the same manner as in Example 1(4). The results are shown in Table 3.

[0468] (6) Abrasion resistance test of inorganic substance layer: Scratch test

[0469] <Example 42>

[0470] Using polysiloxane compound 1, PC as the resin substrate, and SiO2 as the inorganic substance layer, a scratch test was conducted on the inorganic substance layer of the laminate produced in the manner of Example 3 under the following conditions, and the critical load value was measured to evaluate the abrasion resistance of the inorganic substance layer.

[0471] Device used: Micrometer Scratch Tester (CSR-5000) manufactured by Rhesca Co., Ltd.

[0472] Diameter of the indenter (front end needle): 25 μm

[0473] Scratch speed: 10 μm / sec

[0474] Amplitude width: 100 μm

[0475] Marked load: 10 mN / sec

[0476] As a result, the critical load value was 42.1 mN. The results are shown in Table 4. The larger this value, the higher the abrasion resistance.

[0477] <Examples 43 to 56>

[0478] Except for using polysiloxane compounds 1, 5, 9, or 11, using PC, PMMA, or PET as the resin substrate, and using SiO2 or ZrO2 as the inorganic substance layer, laminates were produced in the same manner as in Example 42, and the abrasion resistance of the respective inorganic substance layers was evaluated. The results are shown in Table 4.

[0479] <Example 57>

[0480] Using polysiloxane compound 12, using PC as the resin substrate, after forming a curable composition for inorganic substance lamination on the PC as in Example 29, SiO2 was laminated by ion plating. For the produced laminate, the abrasion resistance of the inorganic substance layer was evaluated in the same manner as in Example 42. As a result, the critical load value was 51.1 mN. The results are shown in Table 4.

[0481] <Example 58>

[0482] Except for using polysiloxane compound 13, a laminate was produced in the same manner as in Example 57, and for this laminate, the abrasion resistance of the inorganic substance layer was evaluated. As a result, the critical load value was 69.3 mN. The results are shown in Table 4.

[0483] <Example 59>

[0484] Using polysiloxane compound 11, with PC as the resin substrate, after forming a cured product for inorganic material lamination on the PC as in Example 34, ZrO2 was laminated by ion plating. For the fabricated laminate, the abrasion resistance of the inorganic material layer was evaluated in the same manner as in Example 42. As a result, the critical load value was 63.9 mN. The results are shown in Table 4.

[0485] <Example 60>

[0486] Using polysiloxane compound 13, with PC as the resin substrate, after forming a cured product for inorganic material lamination on the PC as in Example 35, SiO2 was laminated by ion plating. For the fabricated laminate, the abrasion resistance of the inorganic material layer was evaluated in the same manner as in Example 42. As a result, the critical load value was 68.7 mN. The results are shown in Table 4.

[0487] <Comparative Examples 15 - 19>

[0488] Except for using M - 405 described in Reference Example 1 instead of the polysiloxane compound and using PMMA or PET as the resin substrate, laminates were fabricated in the same manner as in Comparative Example 5 or 6. These laminates had PC, PMMA, or PET as the resin substrate and SiO2 or ZrO2 as the inorganic material layer. In the same manner as in Example 42, the abrasion resistance of each inorganic material layer was evaluated. The results are shown in Table 4.

[0489] <Comparative Examples 20 - 24>

[0490] Except for not using M - 405 described in Reference Example 1, the abrasion resistance of each inorganic material layer was evaluated in the same manner as in Comparative Examples 15 - 19. The results are shown in Table 4.

[0491] (Table 2)

[0492]

[0493]

[0494] (Table 3)

[0495]

[0496] (Table 4)

[0497]

[0498]

[0499] As can be seen from Table 2, the inorganic matter layer-by-layer bottom coatings of the present disclosure all have good adhesion to the resin substrate and the inorganic matter layer. The adhesion (0 - 5) of Examples 1 to 35 to the inorganic matter layer is better than that of Comparative Examples 1 to 6 (6 - 12) when using a bottom coating without polysiloxane and Comparative Examples 7 to 12 (9 - 17) without using a bottom coating, showing excellent adhesion to various resin substrates and various inorganic matter layers.

[0500] In addition, as can be seen from Table 2, the bottom coating containing a polysiloxane compound having T units and D units as structural units has more excellent adhesion to the inorganic matter layer than the bottom coating containing a polysiloxane compound composed only of T units. This can be seen more clearly when comparing cases where all conditions except the polysiloxane compound are the same, for example, comparing Examples 1, 3, and 4 with Examples 5 - 10 and 13 - 15, comparing Examples 18 and 20 with Examples 21, 23, and 24, and comparing Comparative Example 29 with Example 30.

[0501] It should be noted that the adhesion of Example 16 to the inorganic matter layer is also "3", so it is excellent, but the adhesion is slightly worse than that of other substances having T units and D units. From this, it can be known that the value of x / (v + w + x + y) as the proportion of the D unit is preferably less than the ratio 0.69 of the polysiloxane compound 7 contained in Example 16.

[0502] As can be seen from Table 3, the inorganic matter layer-by-layer bottom coatings of the present disclosure still have good adhesion to the resin substrate and the inorganic matter layer even after warm water treatment. The adhesion (0 - 5) of Examples 36 to 41 to the inorganic matter layer is better than that of Comparative Example 13 (25) when using a bottom coating without polysiloxane and Comparative Example 14 (25) without using a bottom coating, showing excellent adhesion after warm water treatment.

[0503] As can be seen from Tables 2 to 4, the inorganic matter layer-by-layer bottom coatings of the present disclosure can both have good adhesion to the resin substrate and the inorganic matter layer and abrasion resistance of the inorganic matter layer of the laminate, with excellent practicality. This can be seen, for example, from the results of Example 42, which is the same laminate as Example 3 in Table 2, and Examples 43 to 60, which are its modification examples. In contrast, Comparative Examples 15 to 19 in Table 4 are all obtained by curing a curable composition containing a polyfunctional monomer without a polysiloxane compound. Although there are cases with high abrasion resistance, the adhesion to the inorganic matter layer is insufficient, so they are not practical. This can be seen, for example, from the results of Comparative Examples 15 and 18, which are the same laminates as Comparative Examples 5 and 6 in Table 2.

[0504] In addition, as can be seen from Table 4, the undercoat layer containing a polysiloxane compound having T units and D units as structural units has more excellent abrasion resistance of the inorganic material layer laminated thereon than the undercoat layer containing a polysiloxane compound composed only of T units. This can be seen more clearly when comparing cases where all conditions other than the polysiloxane compound are the same, for example, comparing Examples 42 to 44 with Examples 45 to 47, Comparative Examples 49 to 51 with Examples 52 to 54, and Comparative Example 57 with Example 58.

[0505] Therefore, the undercoat layer containing a polysiloxane compound having T units and D units as structural units is particularly excellent in both physical properties of adhesion to the inorganic material layer and abrasion resistance of the laminated inorganic material layer, and has more excellent practicality.

[0506] Industrial Applicability

[0507] Examples of the use of the laminate of the present disclosure include, for example, the outer panel portion of automobile bodies such as passenger cars, trucks, motorcycles, and buses; automobile parts; the outer panel portion of household electrical appliance products such as mobile phones and audio equipment.

[0508] In addition, it can be used for packaging materials for moisture-proof required parts or components in various devices such as optical elements, liquid crystal displays or organic EL displays, semiconductor devices, thin-film solar cells, etc., as well as for packaging of foods, clothes, electronic components, etc.

[0509] In addition, it can be used as a decorative printed film laminate, which is useful as a decorative film for display substrates, touch panels, thin films with transparent strip electrodes, lens sheets, optical waveguides, solar cell substrates, optical discs, various transparent substrates, etc.

[0510] Examples of the functions of the inorganic material layer or the laminate include, for example, antireflection, antifogging, gas barrier, hard coating, abrasion resistance, wear resistance, design, antistatic, conductivity, moisture resistance, weather resistance, light resistance, waterproof, oilproof, stainproof, antibacterial, antiviral, anti-bioactivity, ultraviolet resistance, cosmic ray resistance, acid plasma resistance, atomic oxygen resistance, etc.

[0511] The disclosure of Japanese Patent Application No. 2021-017829 filed on February 5, 2021 is incorporated herein by reference in its entirety.

[0512] All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. An inorganic substance layer-by-layer bottom coating agent composition, which is coated on a resin substrate in order to layer inorganic substances on the resin substrate by a dry film-forming method, wherein, The composition contains a polysiloxane compound represented by the following formula (1), a radical polymerization initiator, and / or a cationic polymerization initiator. [Chemical formula 1] In Formula (1), R 1 , R 2 , and R 3 each independently represent an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a monovalent organic group having a (meth)acryloyl group, an epoxy group, or an oxetanyl group. The alkyl group, aralkyl group, aryl group, unsaturated hydrocarbon group, (meth)acryloyl group, epoxy group, and oxetanyl group are optionally substituted with at least one selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyl group, and an oxy group. Among R 1 , R 2 , and R 3 , at least one is a monovalent organic group having a (meth)acryloyl group, an epoxy group, or an oxetanyl group. R 1 , R 2 , and R 3 are the same as or different from each other. In Formula (1), v, w, x, and y each represent the proportion of v, w, x, and y in the total amount. w represents a positive number of 1 or less, v and y each independently represent 0 or a positive number less than 1, and x is a positive number less than 1. Satisfies 0.3 ≤ {w / (v + w + x + y)} ≤ 1.0 and 0 ≤ {x / (v + w + x + y)} < 0.

69.

2. The undercoat agent composition for inorganic material layer-by-layer stacking according to claim 1, wherein, The dry film-forming method is a physical vapor deposition method.

3. The undercoat agent composition for inorganic material layer-by-layer lamination according to claim 1, wherein, Satisfies 0.5 ≤ {w / (v + w + x + y)} ≤ 1.0 and 0 ≤ {y / (v + w + x + y)} ≤ 0.

5.

4. The undercoat agent composition for inorganic material layer-by-layer lamination according to claim 1, wherein, The viscosity of the polysiloxane compound at 25°C is 10 to 1,000,000 mPa·s.

5. A cured product for laminating inorganic substances, which is obtained by curing the inorganic substance laminating primer composition according to any one of claims 1 to 4.

6. A laminate, comprising the cured product for laminating inorganic substances according to claim 5, a resin substrate, and an inorganic substance layer.

7. The laminate according to claim 6, wherein, In the evaluation of the adhesion of the inorganic substance layer to the cured product for laminating inorganic substances in the cross-cut peel test, the number of peeled squares is 5 or less out of 25 squares.

8. A method for producing the cured product for laminating inorganic substances according to claim 5, comprising a step of irradiating the inorganic substance laminating primer composition according to any one of claims 1 to 4 with active energy rays and curing it.

9. The manufacturing method of the laminate according to claim 6 or 7, wherein, Comprises a step of irradiating the inorganic substance laminating primer composition according to any one of claims 1 to 4 with active energy rays and curing it.

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