Resin and method for producing the same, photosensitive resin composition, ultraviolet-curable varnish, semi-adhesive agent, and processing sheet

Abstract

To provide a resin that can form a coating film exhibiting high adhesion even to low-wettability surfaces and demonstrating excellent moisture resistance.SOLUTION: A resin of the present invention is produced by reacting an acrylic polymer (a) having a structural unit derived from a cyclocarbonate group-containing (meth)acrylic monomer with a Si-containing compound (b) having an amino group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin, a method for producing the resin, a photosensitive resin composition, an ultraviolet-curable varnish, a pseudo-adhesive, and a processed sheet. More specifically, the present invention relates to a resin obtained by reacting an acrylic polymer with a Si-containing compound, a method for producing this resin, and a photosensitive resin composition, an ultraviolet-curable varnish, a pseudo-adhesive, and a processed sheet containing this resin. [Background technology]

[0002] Patent Document 1 discloses a two-component low-temperature curing resin composition that contains a carbonate group-containing copolymer as a base resin component and a compound having one amino group and at least one hydrolyzable silyl group in one molecule as a curing agent component. The technology described in Patent Document 1 is said to be able to provide a coating resin composition that has excellent low-temperature curing properties.

[0003] Patent Document 2 discloses a composition for removable adhesive-coated paper, which contains at least one elastomer component selected from rubber elastomers and (meth)acrylolyl group-containing elastomers, having a weight-average molecular weight of 5,000 to 400,000, at least one ultraviolet-curable component selected from ultraviolet-curable oligomers and ultraviolet-curable monomers, and a polymerization initiator.It also describes that a cured layer of this composition is formed in a predetermined portion of the overlapping surfaces of a base paper, and that by bringing the overlapping surfaces into contact with each other and applying a predetermined pressure, removable adhesive-coated paper can be obtained. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 2764995 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-210879 Summary of the Invention [Problem to be solved by the invention]

[0005] Conventional pseudo-adhesive coated papers, such as the removable adhesive coated paper described in Patent Document 2, are required to have a coating formed by curing that has high adhesion even to surfaces with low wettability, for example, due to the inclusion of wax components in toner or ink. In addition, this coating is also required to have excellent moisture resistance, i.e., excellent blocking resistance. However, the conventional compositions and coated papers described above have not been able to meet these requirements.

[0006] The object of the present invention is to provide a resin that can form a film that exhibits high adhesion even to surfaces with low wettability and has excellent moisture resistance, a method for producing the resin, a photosensitive resin composition, an ultraviolet-curable varnish, a pseudo-adhesive, and a processed sheet. [Means for solving the problem]

[0007] The resin according to one aspect of the present invention is obtained by reacting (a) an acrylic polymer having structural units derived from a cyclocarbonate group-containing (meth)acrylic monomer with (b) an Si-containing compound having an amino group.

[0008] A photosensitive resin composition according to one embodiment of the present invention contains the resin, a photopolymerization initiator, and a polymerizable compound.

[0009] An ultraviolet-curable varnish according to one embodiment of the present invention comprises the photosensitive resin composition.

[0010] A pseudo-adhesive according to one embodiment of the present invention comprises the photosensitive resin composition.

[0011] A processed sheet according to one embodiment of the present invention comprises a sheet-like substrate and a pseudo-adhesive film overlapping at least one surface of the sheet-like substrate, the pseudo-adhesive film including a cured product of the pseudo-adhesive.

[0012] A method for producing a resin according to one aspect of the present invention comprises reacting an acrylic polymer (a) having structural units derived from a cyclocarbonate group-containing (meth)acrylic monomer with a Si-containing compound (b) having an amino group. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a resin that exhibits high adhesion even to surfaces with low wettability and can form a film with excellent moisture resistance, a method for producing the resin, as well as a photosensitive resin composition, an ultraviolet-curable varnish, and a pseudo-adhesive. DETAILED DESCRIPTION OF THE INVENTION

[0014] An embodiment of the present invention will be described below. Note that the following embodiment is merely one of various embodiments of the present invention, and the present invention can be modified in various ways depending on the design.

[0015] 1. Overview The resin according to this embodiment (hereinafter also referred to as resin (A)) is a resin obtained by reacting an acrylic polymer (a) having a structural unit derived from a cyclocarbonate group-containing (meth)acrylic monomer with a Si-containing compound (b) having an amino group.

[0016] In order to solve the above problems, the inventors have conducted research and development to form a film that exhibits high adhesion even to surfaces with low wettability, and to improve the moisture resistance of this film.

[0017] It has been known for some time that the inclusion of silicone compounds in UV-curable varnishes tends to improve adhesion to surfaces with low wettability. However, it has been found that the inclusion of silicone compounds in UV-curable varnishes causes blocking, i.e., reduces moisture resistance.

[0018] Therefore, we attempted to improve both adhesion to surfaces with low wettability and moisture resistance by introducing a silicone structure into the acrylic polymer contained in UV-curable varnish. We attempted to introduce the silicone structure into this acrylic polymer by polymerization using (meth)acrylic-modified silicone, but found that severe foaming occurred during polymerization, posing a problem in productivity.

[0019] The resin (A) of the present invention is prepared by introducing a cyclocarbonate group into an acrylic polymer (a) and then reacting the polymer with an Si-containing compound (b) having an amino group, thereby enabling the introduction of a silicone structure into the acrylic polymer (a) without foaming. Resin (A) allows the formation of a coating that exhibits high adhesion even to surfaces with low wettability, and the moisture resistance (blocking resistance) of the coating can be improved. The reason why the present invention achieves the above-mentioned effects by providing the above-mentioned configuration is not entirely clear, but can be presumed as follows, for example. Resin (A) contains a portion derived from the Si-containing compound (b), which allows the coating formed by curing of resin (A) to have improved adhesion even to surfaces with low wettability. Furthermore, the portion derived from the Si-containing compound (b) of resin (A) is integrated with the acrylic polymer (a) through the reaction between the cyclocarbonate group and the amino group. Therefore, bleeding out and loss is suppressed even in high-humidity environments, thereby improving the moisture resistance of the coating.

[0020] 2.Details <Resin> The resin (A) according to this embodiment is a resin obtained by reacting an acrylic polymer (a) having structural units derived from a cyclocarbonate group-containing (meth)acrylic monomer with an Si-containing compound (b) having an amino group. That is, the resin (A) is a reaction product of the acrylic polymer (a) and the Si-containing compound (b). The acrylic polymer (a) and the Si-containing compound (b) will be described below.

[0021] [Acrylic polymer] The term "acrylic polymer" refers to a polymer having, at least in part, a structural unit derived from a (meth)acrylic monomer. The term "(meth)acrylic monomer" refers to a monomer having a (meth)acryloyl group. The acrylic polymer (a) has a structural unit derived from a cyclocarbonate group-containing (meth)acrylic monomer (hereinafter also referred to as structural unit (X)). In other words, the acrylic polymer (a) is a polymerization product of a monomer containing a (meth)acrylic monomer having a cyclocarbonate group. In this specification, "(meth)acrylic" refers to one or both of "acryl" and "methacryl".

[0022] The term "cyclocarbonate group" refers to a group having a carbonate ring, that is, a group having a ring structure containing a carbonate group (-OC(=O)-O-). The cyclocarbonate group is represented, for example, by the following formula (1):

[0023] [ka]

[0024] In the formula (1), R 1 , R 2 and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group, and n is an integer of 0 to 3. When n is 2 or more, multiple R 1 and R 2 may be the same or different. * indicates a bond.

[0025] R 1 , R 2 and R 3 Examples of the hydrocarbon group include alkyl groups such as methyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, and aralkyl groups such as phenethyl groups. Among these, alkyl groups are preferred, and methyl groups are more preferred. 1 , R 2 and R 3is preferably a hydrogen atom. n is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0026] The cyclocarbonate group is preferably a group having a carbonate ring with 4 to 6 ring atoms, more preferably a group having a carbonate ring with 5 or 6 ring atoms, and even more preferably a group having a carbonate ring with 5 ring atoms. Examples of the cyclocarbonate group include a methylene carbonate group, an ethylene carbonate group, a propylene carbonate group, and a trimethylene carbonate group. Of these, an ethylene carbonate group is preferred, and a 2-oxo-1,3-dioxolan-4-yl group is more preferred.

[0027] Examples of cyclocarbonate group-containing (meth)acrylic monomers that provide the structural unit (X) include monomers in which a cyclocarbonate group is bonded to the alkyl group of a (meth)acrylic acid alkyl ester, such as (2-oxo-1,3-dioxolan-4-yl)methyl (meth)acrylate and (2-oxo-1,3-dioxolan-4-yl)ethyl (meth)acrylate.

[0028] The proportion of the structural unit (X) relative to all structural units constituting the acrylic polymer (a) is preferably more than 0% by mass and not more than 20% by mass, more preferably more than 0% by mass and not more than 15% by mass, even more preferably more than 0% by mass and not more than 10% by mass, and particularly preferably more than 0% by mass and not more than 5% by mass, which can further improve the adhesion and moisture resistance of the coating.

[0029] The acrylic polymer (a) may have a structural unit other than the structural unit (X). Examples of the structural unit include a structural unit other than the structural unit (X) that is derived from a hydroxyl group-containing (meth)acrylic monomer (hereinafter also referred to as the structural unit (Y)), and a structural unit other than the structural unit (X) and the structural unit (Y) that is derived from a (meth)acrylic monomer (hereinafter also referred to as the structural unit (Z)). When the acrylic polymer (a) has the structural unit (Y), the adhesion of the coating can be further improved.

[0030] Examples of hydroxyl group-containing (meth)acrylic monomers that provide the structural unit (Y) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, caprolactone (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; hydroxybutyl vinyl ether; hydroxyethyl vinyl ether; and N-hydroxyethyl (meth)acrylamide.

[0031] When the acrylic polymer (a) has the structural unit (Y), the proportion of the structural unit (Y) is preferably more than 0% by mass and not more than 30% by mass, and more preferably more than 0% by mass and not more than 20% by mass, relative to all structural units constituting the acrylic polymer (a). In this case, adhesion can be further improved.

[0032] Examples of (meth)acrylic monomers that provide the structural unit (Z) include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, styrene, α-methylstyrene, o-, m-, and p-methylstyrene, o-, m-, and p-chlorostyrene, vinylnaphthalene, propene, butene, vinylcyclohexane, (meth)acrylonitrile, α-chloro(meth)acrylonitrile, α-ethyl(meth)acrylonitrile, vinylidene cyanide, maleimide, N-alkylmaleimide, and N-phenylmaleimide.

[0033] When the acrylic polymer (a) has the structural unit (Z), the proportion of the structural unit (Z) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more, based on all the structural units constituting the acrylic polymer (a). The proportion of the structural unit (Z) is, for example, 95% by mass or less, based on all the structural units constituting the acrylic polymer (a).

[0034] The acrylic polymer (a) can be synthesized, for example, by polymerizing monomers containing the monomers that give the structural units (X) to (Z) in an inert gas atmosphere such as nitrogen in the presence of a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) and peroxides such as benzoyl peroxide. This polymerization may be carried out in the presence of a solvent such as ethanol, a chain transfer agent such as α-methylstyrene dimer, and the like. The polymerization temperature is, for example, 50°C to 90°C, and the polymerization time is, for example, 1 hour to 24 hours.

[0035] [Si-containing compounds] The Si-containing compound (b) is a Si-containing compound having one or more amino groups. The term "Si-containing compound" refers to a compound having one or more Si atoms. Examples of the Si-containing compound include a compound having a polysiloxane structure (Si-O- structure) and a compound having a hydrolyzable silyl group.

[0036] Examples of the polysiloxane structure include a polydimethylsiloxane structure and a polydiphenylsiloxane structure. The polysiloxane structure may have an aromatic ring. Examples of the aromatic ring include a phenyl group and a naphthyl group.

[0037] Examples of the hydrolyzable silyl group include -SiR a R b R c (R a and R b is an alkoxy group, R c represents a hydrogen atom, an alkyl group, or an alkoxy group), such as a triethoxysilyl group, a trimethoxysilyl group, a diethoxyethylsilyl group, and a dimethoxymethylsilyl group.

[0038] "Amino group" refers to not only unsubstituted amino groups (-NH2 groups) but also substituted amino groups (-NR A R B , R A and R B represents a hydrogen atom or an alkyl group, but both are not hydrogen atoms). From the viewpoint of the reactivity between the Si-containing compound (b) and the acrylic polymer (a), the amino group of the Si-containing compound (b) is preferably an unsubstituted amino group.

[0039] The Si-containing compound (b) may have two or more amino groups. In this case, the resulting resin (A) has an appropriate crosslinked structure, which can further improve the adhesion and moisture resistance of the coating. The number of amino groups in the Si-containing compound (b) is preferably 3 or less, more preferably 1 or 2, and particularly preferably 2.

[0040] Examples of the Si-containing compound (b) include a compound in which an amino group is bonded to a polysiloxane structure such as a polydimethylsiloxane structure (hereinafter also referred to as Si-containing compound (b1)), and a compound in which an amino group is bonded to an alkyl group to which a hydrolyzable silyl group is bonded (hereinafter also referred to as Si-containing compound (b2)).

[0041] Examples of the Si-containing compound (b1) include compounds having two amino groups bonded to each end of a polysiloxane structure. Commercially available products of such compounds include reactive silicone oil (both end type / amino-modified) manufactured by Shin-Etsu Chemical Co., Ltd. and Silaplane (reactive silicone (both end type / amino-modified)) manufactured by JNC Corporation.

[0042] Examples of the Si-containing compound (b2) include monofunctional Si-containing compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.

[0043] The Si-containing compound (b) preferably has an aromatic ring. In this case, the leveling properties of the coating can be further improved. Examples of the Si-containing compound (b) having an aromatic ring include silicone oil having one amino group at each end and a phenyl group in the side chain.

[0044] The amino group equivalent of the Si-containing compound (b) is preferably 100 g / mol or more, more preferably 300 g / mol or more, even more preferably 500 g / mol or more, and particularly preferably 1,000 g / mol or more. The amino group equivalent of the Si-containing compound (b) is, for example, 10,000 g / mol or less, preferably 7,000 g / mol or less, more preferably 5,000 g / mol or less, even more preferably 3,500 g / mol or less, and particularly preferably 2,500 g / mol or less. In these cases, the crosslinking structure in the resin (A) becomes more appropriate, thereby further improving the adhesion of the coating. "Amino group equivalent" refers to the value calculated by (molecular weight of the Si-containing compound (b)) / (number of amino groups in one molecule of the Si-containing compound (b)).

[0045] Resin (A) Resin (A) is obtained by reacting an acrylic polymer (a) with a Si-containing compound (b). Resin (A) is produced when the cyclocarbonate group of the acrylic polymer (a) reacts with the amino group of the Si-containing compound (b) to form a hydroxyalkyl urethane structure.

[0046] Regarding the mixing ratio of the acrylic polymer (a) and the Si-containing compound (b) used in the reaction to synthesize the resin (A), the ratio of the Si-containing compound (b) to the acrylic polymer (a) is preferably 1 equivalent (eq) or less. In other words, the number of moles of amino groups in the Si-containing compound (b) is preferably equal to or less than the number of moles of the structural unit (X) in the acrylic polymer (a). In this case, the crosslinked structure of the resin (A) can be more effectively formed, thereby further improving the adhesion of the coating. The "1 equivalent" of the Si-containing compound (b) refers to the amount of the Si-containing compound (b) having the same number of amino groups as the structural unit (X) in the acrylic polymer (a).

[0047] It is also preferable that the ratio of the Si-containing compound (b) to the acrylic polymer (a) is greater than 1 equivalent (eq), in which case the amino groups of the Si-containing compound (b) remain in the resin (A), thereby further improving the adhesion of the coating formed from the resin (A).

[0048] The resin (A) can be synthesized, for example, by mixing and reacting an acrylic polymer (a) and a Si-containing compound (b). The reaction temperature is, for example, from 20° C. to 150° C., and preferably from 25° C. to 100° C. The reaction time is, for example, from 30 minutes to 24 hours, and preferably from 1 hour to 9 hours.

[0049] The weight average molecular weight (Mw) of resin (A) is preferably 5,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more. The Mw of resin (A) is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less. In these cases, the adhesion and moisture resistance of the coating can be further improved. The Mw of resin (A) is the relative weight average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0050] <Resin manufacturing method> The method for producing the resin (A) of this embodiment involves, for example, reacting an acrylic polymer (a) having a structural unit derived from a cyclocarbonate group-containing (meth)acrylic monomer with a Si-containing compound (b) having an amino group.

[0051] By mixing the acrylic polymer (a) and the Si-containing compound (b) in the above-mentioned mixing ratio and reacting them at the above-mentioned temperature and time, the resin (A) can be obtained simply and reliably without foaming.

[0052] <Photosensitive resin composition> The photosensitive resin composition of this embodiment (hereinafter also referred to as composition (G)) contains the above-mentioned resin (A), photopolymerization initiator (B), and polymerizable compound (C). Composition (G) may further contain other components in addition to the above components, as long as the effects of this embodiment are not impaired.

[0053] When the composition (G) is irradiated with light, the photopolymerization initiator (B) acts to cure the polymerizable compound (C), forming a coating. This coating contains the cured product of the composition (G), and therefore exhibits high adhesion even to surfaces with low wettability and excellent moisture resistance. Each component will be described below.

[0054] [resin] The resin (A) is as described above.

[0055] The proportion of resin (A) is preferably 2% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 25% by mass or less, based on the total solid content of composition (G). The "total solid content" of the composition means the sum of all components other than the solvent.

[0056] [Photopolymerization initiator] The photopolymerization initiator (B) is a component that photocures the polymerizable compound (C). The photopolymerization initiator (B) is preferably one that generates radicals when irradiated with ultraviolet light.

[0057] Examples of the photopolymerization initiator (B) include acylphosphine oxide-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and oxime ester-based photopolymerization initiators.

[0058] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate, (2,4,6-trimethylbenzoyl)bis(p-tolyl)phosphine oxide, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide. , bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like.

[0059] Examples of the α-aminoalkylphenone photopolymerization initiator include 2-methyl-1-[4-methylthiophenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0060] Examples of oxime ester photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), etc. Specific commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 manufactured by BASF Japan, and Adeka Arcles N-1919T, NCI-831E, NCI-930, and NCI-730 manufactured by ADEKA.

[0061] In addition to the photopolymerization initiator (B), the composition (G) may contain an appropriate photopolymerization accelerator, a sensitizer, etc. For example, hydroxyketones such as 1-hydroxycyclohexylphenyl ketone, phenylglyoxylic acid methyl ester, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; benzoin and its alkyl ethers; acetophenones such as acetophenone and benzil dimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxane; The composition may contain at least one component selected from the group consisting of thioxanthones such as benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and bis(diethylamino)benzophenone; xanthones such as 2,4-diisopropylxanthone; α-hydroxyketones such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; and nitrogen-containing compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone. The composition may also contain an appropriate photopolymerization accelerator and sensitizer, such as tertiary amines such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethyl benzoate. Composition (G) may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near-infrared exposure, as needed. Composition (G) may also contain a sensitizer for laser exposure, such as a coumarin derivative such as 7-diethylamino-4-methylcoumarin, a carbocyanine dye, or a xanthene dye.

[0062] The photopolymerization initiator (B) preferably contains an α-aminoalkylphenone-based photopolymerization initiator, and more preferably contains 2-methyl-1-[4-methylthiophenyl]-2-morpholinopropan-1-one.

[0063] The proportion of the photopolymerization initiator (B) is preferably from 1 to 20% by mass, more preferably from 3 to 15% by mass, based on the total solid content of the composition (G).

[0064] [Polymerizable compound] The polymerizable compound (C) is a component that is cured by the action of the photopolymerization initiator (B). Examples of the polymerizable compound (C) include compounds having at least one ethylenically unsaturated group in one molecule.

[0065] Examples of the polymerizable compound (C) include compounds having an ethylenically unsaturated double bond, such as monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0066] Examples of monofunctional (meth)acrylates include (meth)acrylic acid hydrocarbon esters such as butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, and phenoxyethyl (meth)acrylate; hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; (meth)acrylic acid monoether glycol esters such as ethoxy-diethylene glycol (meth)acrylate, methoxy-triethylene glycol (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, methoxy-polyethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and phenoxy-polyethylene glycol (meth)acrylate; Examples thereof include 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, neopentyl glycol-(meth)acrylic acid-benzoate, tetrahydrofurfuryl (meth)acrylate, and 2-acryloyloxyethyl acid phosphate.

[0067] Examples of polyfunctional (meth)acrylates include 6-Hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipropylene glycol di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate difunctional (meth)acrylates such as triethylene glycol di(meth)acrylate, PEG200# di(meth)acrylate, PEG400# di(meth)acrylate, PEG600# di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, bisphenol A EO adduct di(meth)acrylate, and bisphenol A PO adduct di(meth)acrylate; tri- or higher functional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ε-caprolactone-modified pentaerythritol hexa(meth)acrylate; Examples include hydroxypivalic acid neopentyl glycol (meth)acrylic acid adduct. The composition (G) may also contain an epoxy acrylate, a urethane acrylate, or the like as the polymerizable compound (C).

[0068] The proportion of the polymerizable compound (C) is preferably 15% by mass or more and 86% by mass or less, more preferably 25% by mass or more and 83% by mass or less, and even more preferably 40% by mass or more and 80% by mass or less, based on the total solid content of the composition (G).

[0069] [Other ingredients] Composition (G) may contain at least one component selected from the group consisting of other components, such as polymerization inhibitors, adhesion promoters, rheology control agents, surface modifiers, curing accelerators; copolymers of silicones, acrylates, etc.; leveling agents; thixotropic agents; antihalation agents; flame retardants; antifoaming agents; antioxidants; surfactants; fillers, and polymer dispersants. Examples of polymerization inhibitors include p-methoxyphenol and hydroquinone. When composition (G) contains other components, the proportion of the other components relative to the total solid content of composition (G) is, for example, 5% by mass or less.

[0070] Composition (G) can be prepared by mixing and stirring components (A) to (C) and, if necessary, other components, for example, at a temperature of 25°C or higher and 70°C or lower.

[0071] <UV-curing varnish> The ultraviolet-curable varnish of this embodiment is made of the above-mentioned composition (G), which means that the composition (G) can be suitably used as an ultraviolet-curable varnish.

[0072] The ultraviolet-curable varnish of this embodiment can be applied, for example, to a printed sheet, and then the resulting coating is irradiated with ultraviolet light to harden it and form a film, thereby producing, for example, a pseudo-adhesive processed sheet. Examples of ultraviolet light sources include light source lamps such as high-pressure mercury lamps, metal halide lamps, and LEDs. The output density of the light source lamp is, for example, 20 W / cm or more and 500 W / cm or less. The exposure dose (cumulative light amount) is, for example, 10 mJ / cm. 2 More than 500mJ / cm 2 The following is the result.

[0073] The ultraviolet-curable varnish of this embodiment is made of the above-mentioned composition (G), and therefore can form a film with high adhesion even to a sheet printed with a toner containing wax (for example, the surface tension of the toner is 15 mN / m or more), and can also provide this film with excellent moisture resistance.

[0074] <Pseudo adhesive> The pseudo-adhesive of this embodiment is made of the above-mentioned composition (G). That is, the composition (G) can be used as a pseudo-adhesive.

[0075] The pseudo-adhesive of this embodiment can be applied to, for example, a printed sheet, and then cured by irradiating it with ultraviolet light to form a pseudo-adhesive layer.

[0076] The pseudo-adhesive of this embodiment is made of the above-mentioned composition (G), and therefore can form a pseudo-adhesive layer with high adhesion, even to a sheet printed with a toner containing wax (for example, the surface tension on the toner is 15 mN / m or more), and can also provide this pseudo-adhesive layer with excellent moisture resistance.

[0077] <Processed sheet> The processed sheet of this embodiment is a pseudo-adhesive processed sheet, and includes a sheet-like substrate and a pseudo-adhesive film overlying at least one surface of the sheet-like substrate. The pseudo-adhesive film contains a cured product of the pseudo-adhesive described above.

[0078] The sheet-like substrate may be made of various materials, such as paper, plastic sheets, etc. The surface of the sheet-like substrate may be printed in advance, for example, by printing with a toner containing wax, to provide a surface with low wettability.

[0079] The pseudo-adhesive film includes a cured product of the pseudo-adhesive described above. That is, the pseudo-adhesive film can be formed by photo-curing the pseudo-adhesive described above.

[0080] In the processed sheet of this embodiment, the pseudo-adhesive film contains a cured product of the above-mentioned composition (G), so even if the sheet substrate has a surface with low wettability, the adhesion between the pseudo-adhesive film and the surface of the sheet substrate can be increased, and the moisture resistance of this pseudo-adhesive film can be made excellent.

[0081] (summary) As is apparent from the above embodiments, the present disclosure includes the following aspects.

[0082] The resin according to the first embodiment is obtained by reacting (a) an acrylic polymer having structural units derived from a cyclocarbonate group-containing (meth)acrylic monomer with (b) an Si-containing compound having an amino group.

[0083] According to the first aspect, the resin (A) can form a film that exhibits high adhesion even to surfaces with low wettability and has excellent moisture resistance.

[0084] In the resin according to the second embodiment, in the first embodiment, the Si-containing compound (b) has two or more amino groups.

[0085] According to the second aspect, the resulting resin (A) has an appropriate crosslinked structure, and as a result, the adhesion and moisture resistance of the film can be further improved.

[0086] In the resin according to the third aspect, in the first or second aspect, the Si-containing compound (b) contains an aromatic ring.

[0087] According to the third aspect, the leveling properties of the coating can be further improved.

[0088] In the resin according to the fourth aspect, in any one of the first to third aspects, the acrylic polymer (a) has a structural unit derived from a hydroxyl group-containing (meth)acrylic monomer.

[0089] According to the fourth aspect, the adhesion of the coating can be further improved.

[0090] In the resin according to the fifth aspect, in any one of the first to fourth aspects, the weight average molecular weight is 5,000 or more and 200,000 or less.

[0091] According to the fifth aspect, the adhesion and moisture resistance of the coating can be further improved.

[0092] The photosensitive resin composition according to the sixth aspect contains the resin (A) according to any one of the first to fifth aspects, a photopolymerization initiator (B), and a polymerizable compound (C).

[0093] According to the sixth aspect, it is possible to form a film that exhibits high adhesion even to surfaces with low wettability and has excellent moisture resistance.

[0094] The ultraviolet-curable varnish according to the seventh aspect is made from the photosensitive resin composition according to the sixth aspect.

[0095] According to the seventh aspect, it is possible to form a coating that has high adhesion even to a sheet printed with a toner that contains wax, and it is also possible to make this coating have excellent moisture resistance.

[0096] The pseudo-adhesive according to the eighth embodiment is made of the photosensitive resin composition according to the sixth embodiment.

[0097] According to the eighth aspect, a pseudo-adhesive layer having high adhesion can be formed even on a sheet printed with a toner containing wax, and the moisture resistance of this pseudo-adhesive layer can also be made excellent.

[0098] A processed sheet according to a ninth aspect includes a sheet-like substrate and a pseudo-adhesive film overlying at least one surface of the sheet-like substrate. The pseudo-adhesive film includes a cured product of the pseudo-adhesive according to the eighth aspect.

[0099] According to the ninth aspect, even if the sheet substrate has a surface with low wettability, the adhesion between the pseudo-adhesive film and the surface of the sheet substrate can be increased, and the moisture resistance of this pseudo-adhesive film can be made excellent.

[0100] The resin production method according to the tenth aspect comprises reacting an acrylic polymer (a) having structural units derived from a cyclocarbonate group-containing (meth)acrylic monomer with an Si-containing compound (b) having an amino group.

[0101] According to the tenth aspect, the resin (A) can be obtained simply and reliably without foaming. [Example]

[0102] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0103] 1. Resin synthesis In Resin Synthesis Examples A1 to A13 and B1 and B2, a four-neck flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer was prepared, and each raw material was introduced into the four-neck flask in the type and amount (unit: g) shown in "Category a" in Table 1 below, and polymerized at 75°C for 7 hours under a nitrogen atmosphere to obtain each polymer. In Synthesis Examples C1 and C2, the polymerization was difficult due to the generation of bubbles during polymerization. Next, in Resin Synthesis Examples A1 to A13, each of the raw materials shown in "Category b" in Table 1 below was added to each of the obtained polymers, and the mixture was reacted at 90°C for 6 hours to obtain a resin solution (solid concentration: 72% by mass) that was a reaction product of an acrylic polymer having a cyclocarbonate group and a Si-containing compound having an amino group.

[0104] (Category a) BA: Butyl acrylate (molecular weight 128.2) EHMA: 2-ethylhexyl methacrylate (molecular weight 198) HEA: 2-hydroxyethyl acrylate (molecular weight 116.1) HPM: 2-hydroxypropyl methacrylate (molecular weight 144.17) DOMA: (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate (molecular weight 186.16) Acrylic-modified silicone A: JNC Corporation's product number "Silaplane FM-0711" (monofunctional methacrylic group-containing monomer, molecular weight 1,000) Acrylic-modified silicone B: JNC Corporation's product number "Silaplane FM-0721" (monofunctional methacrylic group-containing monomer, molecular weight 5,000) EtOH: Ethanol MSD: α-methylstyrene dimer AIBN: 2,2'-azobisisobutyronitrile

[0105] (Category b) Si-containing compounds (monofunctional) with amino groups: 3-aminopropyltriethoxysilane (molecular weight 221.4) Si-containing compound (bifunctional) with amino groups: "PAM-E" manufactured by Shin-Etsu Chemical Co., Ltd. (reactive silicone oil (both terminals / amino-modified), amino group equivalent weight 130 g / mol) Si-containing compound (bifunctional) B with amino groups: Shin-Etsu Chemical Co., Ltd.'s "KF-8010" (reactive silicone oil (both terminals / amino-modified), amino group equivalent weight 430 g / mol) Si-containing compound (bifunctional) C with amino groups: "X-22-161A" manufactured by Shin-Etsu Chemical Co., Ltd. (reactive silicone oil (both terminals / amino-modified), amino group equivalent weight 800 g / mol) Si-containing compound (bifunctional) D with amino groups: "X-22-161B" manufactured by Shin-Etsu Chemical Co., Ltd. (reactive silicone oil (both terminals / amino-modified), amino group equivalent weight 1,500 g / mol) Si-containing compound (bifunctional) E with amino groups: Shin-Etsu Chemical Co., Ltd.'s "KF-8012" (reactive silicone oil (both terminals / amino-modified), amino group equivalent weight 2,200 g / mol) Si-containing compound (bifunctional) F with amino groups: "X-22-1660B-3" manufactured by Shin-Etsu Chemical Co., Ltd. (reactive silicone oil (both terminals / amino-modified, side chain phenyl type), amino group equivalent weight 2,200 g / mol) Si-containing compound (bifunctional) with amino groups: Shin-Etsu Chemical Co., Ltd.'s "KF-8008" (reactive silicone oil (both terminals / amino-modified), amino group equivalent weight 5,700 g / mol)

[0106] 2. Preparation of photosensitive resin composition In Examples 1 to 13 and Comparative Examples 1 to 4, each photosensitive resin composition was obtained by mixing and stirring the components of the type and amount (parts by mass) shown in Table 2 below in a flask at 50° C. The amounts (parts by mass) of the resin solutions (A1 to A13, B1, B2, C1, and C2) in Table 2 indicate the parts by mass of each resin solution (solid concentration: 72% by mass) used to prepare the photosensitive resin composition. In Comparative Examples 5 and 6, resins C1 and C2 were not evaluated because they foamed strongly during polymerization. Polyether-modified siloxane copolymer: Epoch's "TEGO Glide 100" HDDA: 1,6-hexanediol diacrylate TMPTA: Trimethylolpropane triacrylate TPGDA: Tripropylene glycol diacrylate 907: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one MQ: p-Methoxyphenol

[0107] 3. Evaluation (1) Preparation of test piece 1 The photosensitive resin composition of each example and comparative example was applied to a sheet printed with wax-containing toner (surface tension of the upper surface of the toner: 15 mN / m) using a bar coater to form a coating film with a thickness of 6 μm. This coating film was cured by irradiating it with ultraviolet light to form a film, which was used as a pseudo-adhesive processed sheet, and test piece 1 was produced. A high-pressure mercury lamp (output density: 120 W / cm) was used as the ultraviolet light source, and the exposure dose (cumulative light amount) was 35 mJ / cm. 2 It was decided.

[0108] (2) Preparation of test piece 2 Next, the resulting pseudo-adhesive processed sheet was folded, and the coatings were placed together and pressed at a linear pressure of 490 N / cm (50 kg / cm) to bond them together, thereby producing test piece 2.

[0109] (3) Physical property evaluation 1 The leveling property, gloss and adhesion of the test piece 1 were evaluated.

[0110] (4) Physical property evaluation 2 The adhesiveness, peelability, and moisture resistance of the test piece 2 were evaluated.

[0111] (5) Evaluation items [Leveling] The surface of the coating was observed and the results were evaluated according to the following criteria. A: The surface was uniform, smooth and beautiful. B: There were some irregularities, but the surface was smooth and clean. C: There was unevenness and some unevenness was observed. D: There was a lot of unevenness and irregularities were observed. E: Cracks were observed.

[0112] Gloss Using a digital variable angle gloss meter "UGV-5" manufactured by Suga Test Instruments, the gloss value was measured at an incident angle of 60 degrees and an acceptance angle of 60 degrees, and the results were evaluated according to the following criteria. A: The gloss value was 75 or higher. B: Gloss value was 72 to 74. C: Gloss value was 69 to 71. D: Gloss value was 66 to 68. E: The gloss value was 65 or less.

[0113] [Adhesion] The adhesion was evaluated for three different surface tensions of the upper surface of the toner. Adhesion (I): When the surface tension of the toner surface is 15 mN / m Adhesion (II): When the surface tension of the toner surface is 22 mN / m Adhesion (III): When the surface tension of the toner surface is 35 mN / m Cellophane tape was applied to the surface of the coating processed onto the toner printed surface with finger pressure, and the condition was observed when it was peeled off at a 90 degree angle. The results were evaluated according to the following criteria. A: The coating where the tape was applied, the toner layer, the paper and the surrounding area peeled off. B: The film, toner layer, and paper peeled off from the taped area. C: The film where the tape was applied and part of the toner layer peeled off. D: The film where the tape was applied and a small part of the toner layer peeled off. E: Only the film peeled off.

[0114] [Adhesiveness] The adhesive state of the pseudo-adhesive processed sheet after bonding was evaluated according to the following criteria. A: It is well bonded and does not come off even when bent. B: The adhesive is weaker than A, but it adheres without any problems and the adhesive does not come off even when bent. C: The adhesive adheres, but when bent the adhesive surface peels off slightly. D: Adhesion is achieved but weakly, and the adhesive surface peels off when bent. E: No adhesion at all.

[0115] [Removability] The releasability of the pseudo-adhesive processed sheet after adhesion was evaluated according to the following criteria. A: The sheet peels off smoothly without tearing. B: The sheet peels off without tearing, but the peel strength is slightly higher. C: The sheet peels off without tearing, but the peel strength is so strong that some cracks or streaks appear on the surface. D: The sheet peels off without tearing, but the peel strength is so high that many cracks and streaks appear on the surface. E: It sticks and when you try to remove it the paper tears.

[0116] [Moisture resistance] The pseudo-adhesive processed sheet after adhesion was left for one week in a constant temperature and humidity atmosphere of 50°C and 80% RH, and the peelability thereafter was evaluated as moisture resistance according to the following criteria. A: The sheet peels off smoothly without tearing. B: The sheet peels off without tearing, but the peel strength is slightly higher. C: The sheet peels off without tearing, but the peel strength is so strong that some cracks or streaks appear on the surface. D: The sheet peels off without tearing, but the peel strength is so high that many cracks and streaks appear on the surface. E: It sticks together and if you try to remove it, the paper will tear.

[0117] [Table 1]

[0118] [Table 2]

[0119] The results in Table 2 above show that the photosensitive resin compositions containing the resins of Examples 1 to 13 exhibit high adhesion even to surfaces with low wettability and are capable of forming coatings with excellent moisture resistance.

Claims

1. an acrylic polymer (a) having a structural unit derived from a cyclocarbonate group-containing (meth)acrylic monomer; a Si-containing compound (b) having an amino group; A resin obtained by reacting

2. The Si-containing compound (b) has two or more amino groups. The resin of claim 1.

3. The Si-containing compound (b) contains an aromatic ring. The resin of claim 1.

4. The acrylic polymer (a) further has a structural unit derived from a hydroxyl group-containing (meth)acrylic monomer. The resin of claim 1.

5. The weight average molecular weight is 5,000 or more and 200,000 or less. The resin of claim 1.

6. The resin according to any one of claims 1 to 5, a photopolymerization initiator; Polymerizable compound A photosensitive resin composition comprising:

7. An ultraviolet-curable varnish comprising the photosensitive resin composition according to claim 6.

8. A pseudo-adhesive comprising the photosensitive resin composition according to claim 6.

9. A sheet-like substrate and a pseudo-adhesive film overlapping at least one surface of the sheet-like substrate, The pseudo-adhesive film comprises a cured product of the pseudo-adhesive according to claim 8. Processing sheet.

10. an acrylic polymer (a) having a structural unit derived from a cyclocarbonate group-containing (meth)acrylic monomer; a Si-containing compound (b) having an amino group; React with Resin manufacturing method.

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