Two-liquid type addition curable composition kit

Abstract

To provide a two-liquid type addition curable composition kit for release, capable of freely varying a mixing ratio in use while maintaining a definite curing rate and a range of pot-life though being a two-liquid type, and small in appearance abnormality of a cured product.SOLUTION: A two-liquid type addition curable composition kit is composed of a first liquid and a second liquid, wherein the first liquid contains (A) organopolysiloxane, (C) an inhibitor, (D) a platinum catalyst, and (E) organopolysiloxane which has at least one alkenyl group bonded to a silicon atom on a side chain of a molecular chain, and has an alkenyl group content per one molecule of 1.0 mmol / g or more and viscosity of 100 mPa s or more and 100,000 mPa s or less, wherein a blended amount of the component (E) in the first liquid is such an amount that a molar ratio [an alkenyl group in component (E) / platinum] of the alkenyl group in the component (E) to the platinum atom is 50 or more and 1,000 or less, and the second liquid contains (B) an organohydrogenpolysiloxane.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a two-component addition-curable composition kit containing a first liquid and a second liquid, which is characterized in that even when the first liquid and the second liquid are mixed in any amount, the influence on the curing rate is small, and the appearance abnormality of the cured product due to the discoloration of the first liquid during storage and the curing failure due to the deactivation of the catalyst of the first liquid are less likely to occur. The present invention also relates to a method for producing the two-component addition-curable composition kit and the composition kit.

Background Art

[0002] Addition-curable compositions for forming release materials such as release papers or release films mainly composed of silicone can impart performance such as release characteristics, mold release properties, and water repellency to paper or plastic film substrates by coating various substrate surfaces. For example, in protective films and process release films used for surface protection of adhesive surfaces such as adhesive sheets and for the manufacture of electronic components such as ceramic capacitors, a silicone cured film is formed on the surface of a plastic film substrate, thereby imparting releasability to the plastic film.

[0003] Addition-curable compositions for release mainly composed of silicone are roughly classified into solvent-based, solvent-free, and emulsion-based types, and they are usually stored and sold in a state of being divided into two or three components. Before use, a plurality of liquids (or emulsions) divided into components are mixed, and the resulting composition is coated on various substrate surfaces and cured, whereby a cured product of the addition-curable composition is formed on the substrate surface, and release characteristics are imparted to the substrate surface thereby.

[0004] General addition-curable compositions for release usually contain a polysiloxane containing an alkenyl group as a main agent, an organohydrogenpolysiloxane as a crosslinking agent, a catalyst, an inhibitor, and the like. By changing the addition amount, functional group amount, viscosity, coating amount, etc. of each component, desired release film physical properties can be imparted to the substrate.

[0005] Patent Document 1 discloses an addition-curable organopolysiloxane release coating composition. In Patent Document 1, the coating composition comprises: A) at least one organopolysiloxane having at least two terminal aliphatic unsaturated groups; B) at least one organopolysiloxane crosslinking agent having silicon-bonded hydrogen (“Si-H”), wherein at most 67 mole percent of the siloxy groups in the organopolysiloxane crosslinking agent contain Si-H groups; C) at least one hydrosilylation catalyst; and optionally D) a hydrosilylation inhibitor.

[0006] Such an addition-curable composition for release is usually stored and sold as a two-component composition packaged in two packages. Common methods of packaging into two packages are: (1) a method of packaging into a first liquid containing a main agent, a crosslinking agent, and an inhibitor, and a second liquid containing a catalyst; or (2) a method of packaging into a first liquid containing a main agent and a catalyst, and a second liquid containing a main agent, a crosslinking agent, and an inhibitor. In order to obtain a desired curing rate, it is mainly necessary to keep the mixing ratio of the catalyst and the inhibitor constant. Therefore, when the packaging method (1) is adopted, a predetermined amount of the second liquid is mixed with the first liquid before use. When the packaging method (2) is adopted, the same amount of the second liquid as the first liquid is mixed and used.

[0007] The advantage of such a packaged two-component addition-curable composition is that it is an easy-to-understand system for the user. That is, since the mixing ratio is determined, it can be made usable by adding a specified number of parts of the second liquid to the first liquid, and the operation during mixing becomes simple. Also, since the ratio of the main agent and the crosslinking agent is always constant, there is an advantage that the concern about the variation in physical properties due to the fluctuation of the addition amount is reduced.

[0008] In Patent Document 2, there is also disclosed a two-component addition reaction-curing silicone composition that can be used by mixing two liquids, namely, an emulsion composition containing an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and a catalyst inhibitor, and a silicone emulsion composition containing a catalyst.

[0009] In a two-component composition, it is common for the catalyst and the inhibitor to be packaged separately in different liquids. The inhibitor acts like a catalyst poison. This is because depending on the components, they may interact strongly with the catalyst and deactivate its function. If they are not packaged separately, the one-component composition may turn black and cause abnormal appearance of the product, which is a cured product of the addition-curable composition, or may cause poor curing.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0011] By the way, on the user side using the addition-curable composition for peeling, in order to achieve the desired peeling force, there is a desire to finely adjust the ratio of the main agent (polysiloxane containing an alkenyl group) to the crosslinking agent (organohydrogenpolysiloxane). Also, due to changes in environmental temperature and humidity, etc., the physical properties of the resulting cured product may vary. In contrast, there is also a desire to optimize the physical properties by freely changing the mixing ratio of the two liquids. Thus, there was a need on the user side to change the mixing ratio of the first liquid and the second liquid during use to change the desired physical properties such as the peeling force while maintaining the curing rate and the workable time (pot life). However, in the addition-curable composition for peeling subcontracted by the above method (1) or (2), there is a problem that the mixing ratio of the first liquid and the second liquid is fixed and cannot be adjusted on the user side. If the mixing ratio is changed and the compounding ratio is adjusted for use, there is a problem that the curing rate and pot life during heat curing change due to the change in the compounding ratio of the catalyst and the inhibitor.

[0012] Against the above background, it is an object of the present invention to provide a two-component addition-curable composition kit for peeling that is a two-component type, can freely change its mixing ratio during use while maintaining a certain curing rate and pot life range, and has few appearance abnormalities in the cured product.

Means for Solving the Problems

[0013] In order to solve the above problems, the present inventors have intensively studied and improved the dispersion stability of the platinum complex by blending an organopolysiloxane having a specific alkenyl group, and can significantly prevent a strong interaction with an inhibitor contained in the same system. It has been found that a two-component addition-curable composition kit for peeling can be provided that is a two-component type, can freely change its mixing ratio during use while maintaining a certain curing rate and pot life range, and can thus impart desired peeling film physical properties to a substrate and has few appearance abnormalities in the cured product, and the present invention has been completed.

[0014] That is, the present invention is A two-component addition-curable composition kit comprising a first liquid and a second liquid, The first liquid is (A) component: an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain ends and having a viscosity at 25 ° C. of 10 mPa·s or more and 1,000,000 mPa·s or less, (C) component: an inhibitor, (D) component: a platinum catalyst, (E) Component: An organopolysiloxane having at least one alkenyl group bonded to a silicon atom in a molecular chain side chain, with an alkenyl group content per molecule of 1.0 mmol / g or more and a viscosity at 25 °C of 100 mPa·s or more and 100,000 mPa·s or less, and comprising, The first liquid does not contain organohydrogenpolysiloxane, The blending amount of the (E) component in the first liquid is an amount such that the molar ratio of the alkenyl group to the platinum atom [(alkenyl group in the (E) component / platinum] in the (E) component is 50 or more and 1000 or less, The second liquid is (B) Component: An organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule, The second liquid does not contain the (A) component, the (C) component, the (D) component, and the (E) component, An addition-curable composition can be obtained by mixing the first liquid and the second liquid, which is a two-component addition-curable composition kit characterized by the above. The (C) component may be an alkynol compound. This is because it is easy to disperse in the organopolysiloxane composition and difficult to precipitate. The (D) component may be a platinum vinylsiloxane complex. This is because it has good compatibility with the (A) component and the (E) component and can be stably dispersed.

Advantages of the Invention

[0015] In the two-component addition-curable composition kit having the above-described configuration of the present invention, an organopolysiloxane having a specific alkenyl group as the (E) component is wound around and coordinated between the platinum catalyst as the (D) component containing a platinum complex and the inhibitor as the (C) component, thereby improving the dispersion stability of the platinum complex. Also, due to the steric hindrance of the organopolysiloxane molecules having an alkenyl group as the (E) component in a thread-like form, a strong interaction between the platinum complex of the (D) component and the inhibitor of the (C) component is significantly prevented, etc., and thus the effects of the present invention are considered to be achieved. As a result, it becomes possible to suppress the strong interaction between the platinum complex of the (D) component and the inhibitor of the (C) component, and discoloration during storage of the first liquid is reduced. As a result, it is also possible to suppress appearance abnormalities in the cured product of the addition-curable composition obtained by mixing the first liquid and the second liquid. Further, as a result of suppressing the deactivation of the catalyst of the (D) component contained in the first liquid, curing failure of the cured product is less likely to occur. Furthermore, in the two-component addition-curable composition kit obtained by this formulation, the inhibitor of the (C) component and the platinum catalyst of the (D) component are formulated in the same liquid. For this reason, during use, the mixing ratio of the organopolysiloxane having an alkenyl group contained in the first liquid and the organohydrogenpolysiloxane as the (B) component contained in the second liquid can be adjusted to a desired ratio, and the effect that the curing rate and the pot life can be maintained within a certain range is exhibited.

[0016] Therefore, the two-component addition-curable composition kit of the present invention is a two-component type, and while maintaining the curing rate and the pot life within a certain range, it is possible to change the mixing ratio of the first liquid and the second liquid within a predetermined range. As a result, desired peelable film physical properties can be imparted to the substrate, and also, the cured product is characterized by being less likely to have appearance abnormalities.

Embodiments for Carrying Out the Invention

[0017] The following details of the two-component addition-curable composition kit according to the present invention, the method for producing the composition kit, and the release paper formed using the composition kit will be described. In this specification, for convenience, the combination of this "first liquid" and "second liquid" may also be referred to as a "two-component addition-curable composition".

[0018] The two-component addition-curable composition kit according to the present invention is a two-component addition-curable composition kit comprising a first liquid and a second liquid, The first liquid is (A) component: an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals, with a viscosity at 25 °C of 10 mPa·s or more and 1,000,000 mPa·s or less, (C) component: an inhibitor, (D) component: a platinum catalyst, (E) component: an organopolysiloxane having at least one alkenyl group bonded to a silicon atom in the molecular chain side chain, with an alkenyl group content per molecule of 1.0 mmol / g or more and a viscosity at 25 °C of 100 mPa·s or more and 100,000 mPa·s or less, and the first liquid does not contain organohydrogenpolysiloxane, the blending amount of the (E) component in the first liquid is an amount such that the molar ratio of the alkenyl group to the platinum atom in the (E) component [(alkenyl group in the (E) component / platinum] is 50 or more and 1000 or less, The second liquid is (B) component: an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in one molecule, the second liquid does not contain the (A) component, the (C) component, the (D) component, and the (E) component, an addition-curable composition can be obtained by mixing the first liquid and the second liquid, characterized by this.

[0019] The two-component addition-curing composition kit of the present invention has a first liquid and a second liquid, which are at least two kinds of liquid compositions, and is a kit for obtaining an addition-curing composition by mixing these. In addition to the first liquid and the second liquid, it is also possible to further combine and have a third liquid that does not contain a catalyst or an inhibitor. The above two-component addition-curing composition kit only needs to finally have the first liquid and the second liquid, and depending on circumstances such as storage and transportation, one or both of the first liquid and the second liquid can be further sub-packaged. For example, the first liquid can be sub-packaged and stored as a first premixed liquid containing component (C) and component (E) and a second premixed liquid containing component (D) and component (E), and before mixing with the second liquid, the first premixed liquid and the second premixed liquid can be mixed to obtain the first liquid.

[0020] ((Component (A)) Note that the first liquid may further contain, as component (A), an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain ends and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less, and the second liquid may not contain the above (A). Component (A) is a cross-linking component for forming a cured product by an addition-curing reaction between an SiH group and an alkenyl group together with component (B) described later. Component (A) is an organopolysiloxane having an average composition formula represented by general formula (1) and having two or more alkenyl groups bonded to silicon atoms only at the molecular chain ends. The organopolysiloxane of component (A) is hereinafter also referred to as the alkenyl organopolysiloxane of component (A). [Chemical formula] (In formula (1), R 1 are each independently a hydroxyl group or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and the monovalent hydrocarbon group is a monovalent hydrocarbon group that is substituted or unsubstituted and does not have an aliphatic unsaturated bond, R 11is an alkenyl group having 2 to 10 carbon atoms, a is an integer of 2 or more, b is an integer of 1 or more, c is an integer of 0 or more, and d is an integer of 0 or more. a + b + c + d is not particularly limited as long as it satisfies the above viscosity range, and may be 10 or more and 3,000 or less, preferably 20 or more and 2,000 or less, and more preferably 50 or more and 1,000 or less.

[0021] The alkenyl group R in component (A) 11 Examples thereof include alkenyl groups having 2 to 8 carbon atoms such as vinyl group, allyl group, 1-butenyl group, 1-hexenyl group, etc., preferably vinyl group and allyl group, and particularly preferably vinyl group. These alkenyl groups react with component (B) described later to form a network structure. The alkenyl group is present in an average of about 2, preferably 1.6 or more and 2.2 or less, in the molecule of the alkenyl organopolysiloxane which is component (A).

[0022] When R bonded to the silicon atom in component (A) 1 is a monovalent hydrocarbon group, specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.; aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, etc.; aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group, etc.; substituted hydrocarbon groups in which part or all of the hydrogen atoms in these hydrocarbon groups are substituted by halogen atoms, cyano groups, etc., such as chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group, dibromophenyl group, tetrachlorophenyl group, difluorophenyl group, β-cyanoethyl group, γ-cyanopropyl group, β-cyanopropyl group, etc. Particularly preferred monovalent hydrocarbon groups are methyl group and phenyl group.

[0023] (A) The alkenyl organopolysiloxane component may be linear, branched, or a mixture thereof.

[0024] (A) The component may further include those having -SiOH groups at a part of the molecular chain terminals. In this case, the ratio of the number of silicon atoms having OH groups to the total number of terminal silicon atoms possessed by all the organopolysiloxanes in the (A) component is less than 5%, preferably less than 2%. If the ratio satisfies the above conditions, addition polymerization proceeds sufficiently and a sufficient cured film can be obtained.

[0025] (A) The viscosity of the alkenyl organopolysiloxane component at 25°C is 10 mPa·s or more and 1,000,000 mPa·s or less, preferably 20 mPa·s or more and 500,000 mPa·s or less, and more preferably 50 mPa·s or more and 50,000 mPa·s or less. If the viscosity of the above (A) component is too low, it is likely to volatilize and the formulation is likely to become unstable. If the viscosity of the above (A) component is too high, the resulting silicone composition is likely to be extremely lacking in fluidity, and there is a risk of deterioration of coating workability. Also, in the case of emulsification, the dispersion and emulsification properties by mechanical stirring decrease, and there is a risk of causing poor emulsification.

[0026] Also, for adjusting the physical properties of the final cured film and the viscosity during emulsification, the (A) component may include organopolysiloxanes having two or more types of alkenyl groups with different viscosities. In this specification, the viscosity refers to the value of the absolute viscosity measured by a B-type rotational viscometer at 25°C (the same shall apply hereinafter in this specification).

[0027] This alkenyl organopolysiloxane of component (A) can be produced by methods known to those skilled in the art. For example, it can be produced by the condensation and / or ring-opening polymerization of linear and / or cyclic low molecular weight siloxanes using acid catalysts such as sulfuric acid, hydrochloric acid, nitric acid, activated clay, tris(2-chloroethyl) phosphite, or base catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-butylphosphonium hydroxide, sodium silanolate, potassium silanolate.

[0028] Regarding the blending amount of component (A), when the solid content in the first liquid is 100 parts by mass, it is preferably 5 parts by mass or more and 95 parts by mass or less, more preferably 50 parts by mass or more and 90 parts by mass or less, and even more preferably 60 parts by mass or more and 85 parts by mass or less. Here, the solid content is the total amount of components excluding the water component (the same applies hereinafter in this specification).

[0029] ((B) component) Component (B) in the present invention is an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in one molecule, and is a cross-linking component for forming a cured product by an addition curing reaction between the SiH group and the alkenyl group.

[0030] The organohydrogenpolysiloxane as component (B) is represented by the following average composition formula (2). [Chemical formula] (In formula (2), R 2 are, independently of each other, a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. However, it contains two or more hydrogen atoms bonded to silicon atoms in one molecule, a is an integer of 2 or more, b is an integer of 1 or more, c is an integer of 0 or more, and d is an integer of 0 or more. a + b + c + d is not particularly limited as long as it satisfies the viscosity range described below, and it may be 5 or more and 600 or less, or it may be 10 or more and 400 or less.)

[0031] (B) The viscosity at 25°C of the component may be 1 mPa·s or more and 3,000 mPa·s or less, preferably 10 mPa·s or more and 1,000 mPa·s or less. If the viscosity of the (B) component is within the above range, it is possible to suppress the phenomenon that the (B) component volatilizes before the curing reaction with the alkenyl group in the (A) component and the (E) component proceeds sufficiently, or the curability deteriorates due to low reactivity with the alkenyl group in the (A) component and the (E) component.

[0032] (R bonded to the silicon atom in the (B) component 2 When is another monovalent hydrocarbon group, specifically, the monovalent hydrocarbon group is an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.; a cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.; an aryl group such as phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, etc.; an aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group, etc.; a substituted hydrocarbon group in which part or all of the hydrogen atoms in these hydrocarbon groups are substituted by a halogen atom, a cyano group, etc., such as chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group, dibromophenyl group, tetrachlorophenyl group, difluorophenyl group, β-cyanoethyl group, γ-cyanopropyl group, β-cyanopropyl group, etc. Particularly preferred monovalent hydrocarbon groups are methyl group and phenyl group.

[0033] The blending amount of component (B) in the composition of the present invention is blended according to the amount of alkenyl in component (A) and component (E). For example, when the ratio of the number of alkenyl groups (NA) bonded to silicon atoms in component (A) and component (E) to the number of hydrogen atoms (NH) bonded to silicon atoms contained in component (B) is represented by (NH / NA) (hereinafter referred to as "hydrogen-alkenyl ratio (NH / NA)"), the blending amount of component (B) may be an amount that satisfies 1.0 ≦ (NH / NA) ≦ 6.0, and preferably may be an amount that satisfies 1.3 ≦ (NH / NA) ≦ 4.0. If the blending amount of component (B) is such that the ratio is within the above range, a good cured film with stable peel strength and little transferability of the release agent to the object to be released can be obtained. Generally, when the value of the above ratio (NH / NA) exceeds the above range and becomes large, the amount of unreacted SiH groups remaining in the cured product increases, which not only causes a significant increase in the peel strength but also tends to increase the variation in the peel strength due to the interaction with the adhesive. Similar to component (A), component (B) is also produced by a method known to those skilled in the art.

[0034] Component (B) can further contain those having -SiOH groups at a part of the molecular chain terminals. In this case, the ratio of the number of silicon atoms having OH groups to the total number of terminal silicon atoms of all organopolysiloxanes in component (B) is less than 5%, preferably less than 2%. If the ratio satisfies the above conditions, the addition polymerization proceeds sufficiently, and a sufficient cured film can be obtained.

[0035] In the present invention, the component (A), the component (B), and the component (E) described later may further contain octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylmethylcyclohexasiloxane (D6). The total mass of the components of D4, D5, and D6 is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, and even more preferably 500 mass ppm or less with respect to the total mass of the component (A), the component (B), and the component (E). If the total mass of the said components satisfies the above conditions, the storage stability and the emulsion stability of each liquid in the composition of the present invention obtained will be further improved.

[0036] ((C) component) The component (C) in the present invention is an inhibitor, and in particular, the component (C) is a hydrosilylation reaction inhibitor. The inhibitor which is the component (C) can be used for adjusting the curing rate and the working time (pot life) during the heat curing of the composition. Examples of the inhibitor as the component (C) include alkynols (i.e., acetylene-based alcohols), ketones, enyne compounds, organic phosphorus compounds, and organic nitrogen compounds. Specific alkynols include, for example, methylbutynol, dimethylhexynol, ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 1-propyn-3-ol, 1-butyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, and 4-ethyl-1-octyn-3-ol. Specific enyne compounds include, for example, 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne. Also, maleates (for example, diallyl maleate, bismaleate, or n-propyl maleate) can be mentioned as the component (C). These inhibitors can be used alone or in combination of two or more.

[0037] Particularly, as the component (C), an alkynol compound is preferable. This is because the alkynol compound is liquid in the generally used temperature range, is difficult to precipitate, is easily dispersed in the first liquid, and can maintain a good dispersed state even after mixing with the second liquid, so it is preferable. Although there is no particular limitation, ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 4-ethyl-1-octyn-3-ol, etc. are preferable.

[0038] The blending amount of the hydrosilylation reaction inhibitor of the component (C) can be appropriately selected in consideration of the type of the hydrosilylation reaction inhibitor, the characteristics and blending amount of the hydrosilylation reaction catalyst, the amount of the alkenyl group in the components (A) and (E), and the amount of the silicon atom-bonded hydrogen atom in the component (B). Usually, when the solid content in the first liquid is 100 parts by mass, it is in the range of 0.001 to 2.0 parts by mass, and preferably in the range of 0.01 to 1.5 parts by mass.

[0039] (Component (D)) (D) component can be used as a hydrosilylation catalyst and is a platinum catalyst. () The platinum catalyst has high reactivity and is suitable. Examples of platinum compounds as platinum catalysts include platinum halides (e.g., PtCl4, H2PtCl4·6H2O, NA2PtCl4·4H2O, reaction product of H2PtCl4·6H2O and cyclohexane), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes (e.g., platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), bis-(γ-picoline)-platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride), bis(alkynyl)bis(triphenylphosphine)platinum complex, bis(alkynyl)(cyclooctadiene)platinum complex, etc. Also, the hydrosilylation catalyst as a platinum catalyst can be used in a microencapsulated form. In this case, in order to form fine particle solids that contain the catalyst and are insoluble in the polyorganosiloxane, for example, a thermoplastic resin (e.g., polyester resin or silicone resin) can be used. Also, the platinum catalyst can be used in the form of an inclusion compound, for example, included (encapsulated) in cyclodextrin. It may also be fixed to a particulate carrier material (e.g., activated carbon, aluminum oxide, silicon oxide).

[0040] Particularly, as the (D) component in the present invention, a platinum-vinylsiloxane complex is suitable. (Examples of the platinum-vinylsiloxane complex include a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.) Such a platinum-vinylsiloxane complex has good compatibility with the organopolysiloxanes of the (A) component and the (E) component and can be stably dispersed.

[0041] (D) The blending amount of the component is an effective amount according to the curing temperature and curing time desired depending on the use, but usually, as the concentration of the catalytic metal element with respect to the total mass of the first liquid (in the case of an emulsion type composition, the first liquid containing water), it is preferably in the range of 0.5 to 1,000 mass ppm, more preferably 1 to 500 mass ppm, and still more preferably 5 to 200 mass ppm. When the blending amount is less than 0.5 mass ppm, the addition reaction becomes extremely slow. On the other hand, when the blending amount exceeds 1,000 mass ppm, the cost increases, which is not economically preferable.

[0042] In addition to the platinum catalyst of component (D), a platinum group-based catalyst may also be used in combination. The platinum group-based catalyst that can be used in combination with component (D) consists of a platinum group-based metal or a compound containing this metal. Examples of the metal constituting the platinum group-based catalyst include rhodium, palladium, ruthenium, iridium, etc., and catalyst compounds containing these metals can be used.

[0043] ((E) component) The (E) component in the present invention is an organopolysiloxane having at least one or more alkenyl groups bonded to a silicon atom on the side chain of the molecular chain and having a viscosity at 25 ° C of 100 mPa·s or more and 100,000 mPa·s or less. The viscosity of the (E) component is more preferably in the range of 150 to 80,000 mPa·s, particularly preferably in the range of 200 to 50,000 mPa·s. Also, the blending amount in the composition is an amount such that the molar ratio of the alkenyl group to the platinum atom [(alkenyl group in component (E) / platinum] in the (E) component is 50 or more and 1000 or less. Also, the above (E) component can also be represented by the following general formula (3). [Chemical formula] (In formula (3), R 3 are, independently of each other, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms. However, R 3At least one of them is an alkenyl group having 2 to 10 carbon atoms, and has at least one alkenyl group bonded to a silicon atom on the side chain of the molecular chain. a is an integer of 2 or more, b is an integer of 1 or more, c is an integer of 0 or more, and d is an integer of 0 or more. a + b + c + d is not particularly limited as long as it satisfies the above viscosity range, and may be 80 or more and 1,500 or less, may be 100 or more and 1,200 or less, or may be 150 or more and 1,000 or less. In addition, the alkenyl organopolysiloxane represented by the general formula (3) preferably has at least 3 alkenyl groups on average per molecule.

[0044] Examples of the alkenyl group in the (E) component include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, 1-butenyl group, 1-hexenyl group, etc., preferably vinyl group and allyl group, and particularly preferably vinyl group. These alkenyl groups react with the (B) component to form a network structure.

[0045] The number of alkenyl groups in one molecule is not particularly limited as long as it is 1 or more on the side chain of the molecular chain, but is 3 or more in the molecule of the (E) component, and the alkenyl group content per molecule is preferably 1.0 mmol / g or more. The upper limit of the alkenyl group content is not particularly limited, but if it is 1.0 mmol / g or more and 5.0 mmol / g or less, the crosslinking density does not become too high, which is preferable. Such an alkenyl group is bonded to at least one silicon atom on the side chain of the molecular chain, and the other alkenyl groups may be bonded to the silicon atom at the end of the molecular chain or may be bonded to the silicon atom on the side chain of the molecular chain.

[0046] (E) The other monovalent hydrocarbon groups bonded to the silicon atoms in the component are specifically alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.; aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, etc.; aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group, etc.; substituted hydrocarbon groups in which part or all of the hydrogen atoms in these hydrocarbon groups are substituted by halogen atoms, cyano groups, etc., such as chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group, dibromophenyl group, tetrachlorophenyl group, difluorophenyl group, β-cyanoethyl group, γ-cyanopropyl group, β-cyanopropyl group, etc. Particularly preferred monovalent hydrocarbon groups are methyl group and phenyl group.

[0047] (E) The alkenyl organopolysiloxane of the component may be linear, branched, or a mixture thereof.

[0048] (E) The component may further contain those having -SiOH groups at a part of the molecular chain terminals. In this case, the ratio of the number of silicon atoms having OH groups to the total number of terminal silicon atoms of all the organopolysiloxanes in the (E) component is less than 5%, preferably less than 2%. If the ratio satisfies the above conditions, the addition polymerization can proceed sufficiently and the peeling-off can be suppressed.

[0049] This alkenyl organopolysiloxane of component (E) can be produced by methods known to those skilled in the art. For example, it can be produced by condensation and / or ring-opening polymerization of linear and / or cyclic low molecular weight siloxanes using acid catalysts such as sulfuric acid, hydrochloric acid, nitric acid, activated clay, tris(2-chloroethyl) phosphite, or base catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-butylphosphonium hydroxide, sodium silanolate, potassium silanolate.

[0050] As described above, the blending amount of component (E) is such that the ratio of the alkenyl group in component (E) to the platinum atoms contained in the first liquid, [(alkenyl group (mol) in component (E) / platinum atom (mol))], is 50 or more and 1,000 or less, preferably 70 or more and 800 or less, more preferably 80 or more and 500 or less, and even more preferably 100 or more and 400 or less. If component (E) is blended in such an amount that the above ratio is within the said range, deactivation of the platinum catalyst can be prevented and the influence on the physical properties of the cured film is also small. For example, in 100 parts by mass of the first liquid, 10 parts by mass of component (E) having a molecular weight of 1,000 and containing 10 alkenyl groups in the molecule is blended, and the amount of platinum atoms in the first liquid is 1.0×10 -3 mol. In this case, [(alkenyl group (mol) in component (E))] / [platinum atom (mol)] is [(10×10 / 1000 (mol))] / [1.0×10 -3 (mol)] = 100.

[0051] (Component (F)) The first liquid and the second liquid of the two-component addition-curable composition kit of the present invention may be solvent-free type, or may be an emulsion type in which they are emulsified. In the case of the emulsion type, the first liquid and the second liquid each further contain an emulsifier as component (F) and water as component (G). (F) component, as an emulsifier, a nonionic surfactant or a protective colloid is particularly preferred. When a protective colloid is used as the (F) component, an emulsion having high stability and a release film having a more stable release force after curing can be obtained.

[0052] When a cationic or anionic surfactant, which is an ionic surfactant, is used as the emulsifier of the (F) component, the surfactant remaining on the film surface may adhere to the electronic component and affect the performance (for example, the occurrence of charge-up phenomenon). Therefore, when applying the two-component addition-curable composition kit for release of the present invention to a release film used for electronic component applications, it is particularly preferable to use a protective colloid having low ionicity such as polyvinyl alcohol or a nonionic surfactant.

[0053] Examples of the protective colloid of the (F) component include polymer compounds such as unmodified polyvinyl alcohol, acetylacetylated polyvinyl alcohol, ethylene-modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide or polycarboxylic acid, and alkali metal salts and / or ammonium salts thereof. Unmodified polyvinyl alcohol having low ionicity is particularly preferable for suppressing the above charge-up phenomenon.

[0054] The HLB value representing the balance between hydrophilicity and lipophilicity of the nonionic surfactant used as the (F) component may be 8.0 to 19.0, preferably 10.0 to 18.0, and more preferably 10.0 to 16.0. When a nonionic surfactant having an HLB value within the above range is used, the storage stability and dilution stability tend to be higher. In addition, a surfactant having a low HLB value may be used in combination as other emulsion aids.

[0055] Examples of such nonionic surfactants include sorbitan fatty acid esters, glycerin fatty acid esters, decaglycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol pentaerythritol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene alkylamine fatty acid amides, polyalkyl glycosides, and the like. These nonionic surfactants are preferable in terms of safety, stability, and cost. Particularly from the viewpoint of emulsion stability, polyoxyethylene alkyl ethers are preferable. Note that the nonionic surfactant can be used alone or in combination of two or more kinds.

[0056] When the first liquid and the second liquid of the two-component addition-curable composition kit of the present invention are in emulsion form, the content of component (F) in the first liquid and the second liquid is preferably 1 to 10 parts by mass. If it is less than 1 part by mass, emulsification is difficult, and if it exceeds 10 parts by mass, the viscosity of the aqueous emulsion composition becomes high and the handleability deteriorates. The content of component (F) is more preferably 3 to 6 parts by mass.

[0057] ((Component (G)) Component (G) is water. Although not particularly limited, it is preferable to use ion-exchanged water. The pH of the ion-exchanged water is preferably pH 2.0 to 12.0, particularly preferably pH 4.0 to 10.0. Although it is not recommended to use mineral water, if used, it is preferably used in combination with a metal deactivator or the like. The addition amount of water as component (G) used in emulsification is 20 to 80 parts by mass, preferably 35 to 70 parts by mass, when the total amount of the two-component addition-curable composition of the present invention is 100 parts by mass.

[0058] When the two-component addition-curable composition of the present invention is an emulsion-type composition, the composition is stable against dilution with water and can be further diluted after its preparation. There is no particular limitation on the amount of water (dilution water) used for dilution. When the solid content of the composition is high, there is a tendency for less repulsion when applying to a substrate, and when the solid content is low, it is easy to obtain a good coating appearance in the cured release film. Therefore, the amount of dilution water can be determined according to the balance of these physical properties. When the two-component addition-curable composition of the present invention is a water-in-oil silicone emulsion, since the composition is a water solvent system, it is preferable also from the viewpoint of environmental consideration as compared with a system using an organic solvent.

[0059] When the two-component addition-curable composition of the present invention is of the emulsion type, in its production, emulsification can be carried out by mixing and emulsifying the above components using a commonly used mixer suitable for the production of emulsions, such as a homogenizer, a colloid mill, a homomixer, a high-speed stator-rotor stirring device, etc. Emulsification can be carried out by mixing and stirring (A) component or (B) component, (F) component, and all or part of (G) component which is water to prepare a water-in-oil emulsion, and then adding the remaining water and stirring to obtain a water-in-oil emulsion. In this way, the method of first forming a water-in-oil emulsion and then forming a water-in-oil emulsion is preferable in terms of easy adjustment of the emulsion particle size and the stability of the emulsion.

[0060] When the two-component addition-curable composition of the present invention is of the emulsion type, a preservative may be incorporated into the first liquid. Preservatives are mainly used for the purpose of preventing the propagation and growth of bacteria and fungi and maintaining the quality. There is no particular limitation on the preservative, and existing ones can be used. In particular, preservatives approved as food additives and those with a long-term usage record are considered to have low toxicity to the human body within the upper limit range of the allowable compounding amount, and thus can be preferably used. Specific examples of preservatives include benzoic acid, sodium benzoate, parabens, salicylic acid, sodium salicylate, sorbic acid, potassium sorbate, phenoxyethanol, etc.

[0061] When the two-component addition-curable composition of the present invention is an emulsion type, a pH adjuster may be added to the second liquid. The pH adjuster is used for the purpose of maintaining the pH of the coating material within an arbitrary pH range and retaining the quality. As the pH adjuster, an acid, a base, a salt, or a buffer obtained by combining these can be used according to the purpose. Existing pH adjusters can be used, but components that act as catalyst poisons are not suitable. For example, it is not suitable to use compounds containing nitrogen such as amines and azo compounds, and other compounds containing sulfur, tin, phosphorus, etc. as the pH adjuster in the addition-curing system. In the composition of the present invention, since the pH adjuster is applied to the second liquid containing organohydrogenpolysiloxane, it is preferable to use an acid or an acidic salt as the pH adjuster. Examples include malic acid, lactic acid, acetic acid, adipic acid, citric acid, tartaric acid, and the like.

[0062] (Method for producing a two-component addition-curable composition kit) The two-component addition-curable composition kit of the present invention a main agent blending step of blending an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals as the component (A) and having a viscosity at 25 ° C of 10 mPa·s or more and 1,000,000 mPa·s or less, a catalyst protection step of mixing the component (E) and the component (D) to obtain a protected catalyst, a protected catalyst composition production step of mixing the protected catalyst and the component (C) to obtain a first liquid which is a protected catalyst composition, including a first liquid production step, a second liquid production step of producing a second liquid containing the component (B), and by the production method, a two-component addition-curable composition kit having a first liquid and a second liquid can be produced.

[0063] Specifically, for example, the (E) component and the (D) component are mixed using a stirrer such as a planetary mixer or a console mixer to obtain a protected catalyst through a catalyst protection step. After that, the (C) component and the protected catalyst are mixed using a stirrer such as a planetary mixer or a console mixer to go through a protected catalyst composition manufacturing step, and the first liquid can be adjusted. The main agent blending step can be at any timing. The protected catalyst may be mixed with the (A) component (the catalyst protection step is carried out after the main agent blending step), the main agent blending step may be carried out after the catalyst protection step, or the main agent blending step may be carried out after the protected catalyst composition manufacturing step. In addition, the protected catalyst in this specification is a catalyst in a state where the (E) component is coordinated so as to surround the platinum catalyst of the (D) component in a thread-like manner. It is considered that it is possible to suppress the strong interaction between the inhibitor of the (C) component and the platinum catalyst of the (D) component, and at the same time improve the dispersion stability of the platinum catalyst of the (D) component. Therefore, the protected catalyst composition obtained through the first liquid manufacturing step contains the above (E) component, the above (D) component, and the above (C) component. Also, for the second liquid, it can be adjusted by mixing one or more (B) components using a similar stirrer.

[0064] Moreover, the two-component addition-curable composition of the present invention can also be an emulsion-type two-component addition-curable composition. As a method for manufacturing such an emulsion-type two-component addition-curable composition kit, for example, the following steps: A main agent blending step of blending an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule only at the molecular chain ends of the (A) component and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less, After passing through a catalyst protection step of obtaining a protected catalyst by mixing the component (E) and the component (D) using a stirrer such as a planetary mixer or a console mixer, through a protected catalyst composition production step of obtaining a protected catalyst composition by mixing the component (C) with the protected catalyst using a stirrer such as a planetary mixer or a console mixer, a first liquid emulsification step of adding water of the component (F) and the component (G) to this protected catalyst composition to obtain a first emulsion; A production method including a second emulsification step of obtaining a second emulsion containing the component (B), the component (F), and the component (G) may be mentioned. In the first emulsification step, emulsification can be carried out by a phase inversion method using a high-shear capable stirring device such as a high-speed stirrer typified by a planetary mixer or a homomixer, an ultrasonic homogenizer, or a high-pressure homogenizer. Regarding the component (F) and the component (G), as described above, the entire amount may be added all at once, but a method may also be used in which a part is added and mixed first to adjust the emulsion, and then the remainder is added and mixed to cause phase inversion. Also, an appropriate amount may be left as the remainder, and this component (G) may be added last for dilution and adjustment. Regarding the second emulsification step as well, using a similar stirrer, one or a plurality of the component (B), a part of the component (F), and the component (G) may be added first and mixed and emulsified, and the remaining component (G) may be added later for dilution and adjustment. Although not specified in each explanatory part in some cases, each component may be used alone or in combination of two or more.

[0065] The present invention also provides a release material such as a release paper or a release film including a thin layer base material such as paper or plastic and a cured film formed by curing the two-component addition-curable composition of the present invention. The material serving as the base material in the release material of the present invention is not particularly limited, and may be paper, plastic, glass, metal, cloth, or the like. Examples of the paper include high-quality paper, coated paper, art paper, glassine paper, polyethylene laminated paper, kraft paper, Japanese paper, synthetic paper, and the like.

[0066] Examples of the plastic material include polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polyester, polyimide, polyamide, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polytetrafluoroethylene, polystyrene, polymethylpentene, ionomer, polyacrylate, polymethacrylate, nylon ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, triacetyl cellulose, polyetheretherketone, polyethersulfine, polyphenylene sulfide, polyurethane, polyetherimide, modified polyphenylene ether, polyetheretherketone, polyacrylonitrile, norbornene, cycloolefin, cellophane, and the like. There are no particular restrictions on the type of glass, etc., and it may be chemically strengthened or the like. Glass fiber can also be applied, and the glass fiber may be used alone or in combination with other resins. Examples of the metal include aluminum foil, copper foil, gold foil, silver foil, nickel foil, and the like. The thin-layer substrate in the present invention can be used for a release material used for a protective film of an adhesive sheet, a release film for an electronic component manufacturing process, etc. Therefore, its thickness is not particularly limited as long as it is the thickness of a thin-layer material used for these applications.

[0067] The two-component addition-curable composition kit of the present invention can mix the first liquid and the second liquid at a desired mixing ratio. Although there are no particular restrictions, as described above, the ratio of the number (NA) of alkenyl groups bonded to silicon atoms in the (A) component and the (E) component in the first liquid to the number (NH) of hydrogen atoms bonded to silicon atoms contained in the (B) component in the second liquid, that is, the hydrogen-alkenyl ratio (NH / NA) defined above can be adjusted within a range that satisfies 1.0 ≦ (NH / NA) ≦ 6.0, and preferably an amount that satisfies 1.3 ≦ (NH / NA) ≦ 4.0.

[0068] The two-component addition-curable composition kit of the present invention may be applied to a substrate by a known method after mixing the first liquid and the second liquid (in the case of an emulsion-type two-component addition-curable composition kit, after mixing the first emulsion and the second emulsion). Further, depending on the application, the two-component addition-curable composition may be applied to one side of the substrate or both sides thereof. Examples of known coating methods include roll coating, reverse roll coating, gravure coating, reverse gravure coating, brush coating, spray coating, air knife coating, dipping, bar coating, spin coating, blade coating, gate roll coating, and meniscus coating.

[0069] In the present invention, the thickness of the coating film after applying the two-component addition-curable composition to the substrate and drying is not particularly limited, but may be, for example, 0.01 to 1 μm. From the viewpoint of improving transparency and reducing costs by reducing the thickness of the coating film, the thickness of the coating film is preferably 0.01 to 0.5 μm, particularly preferably 0.01 to 0.3 μm.

[0070] The two-component addition-curable composition of the present invention forms a release film on the substrate after being applied to the substrate, dried, and the curing reaction proceeds. The curing reaction can be carried out at room temperature (for example, 25 °C), but it is also possible to accelerate the curing reaction by heating for about several seconds to several hours. The heating temperature for promoting the effect is not particularly limited, and can be carried out, for example, at 70 °C or higher. The upper limit temperature of heating may be determined according to the thermal decomposition temperature of the organopolysiloxane, and may be, for example, 250 °C or lower. The upper limit temperature can also be determined according to the heat resistance temperature of the substrate, etc., and may be, for example, 150 °C, or may be 100 °C. The curing reaction acceleration treatment by heating can be carried out by a usual method such as a heating roll, a heating drum, or a hot air drying furnace.

Examples

[0071] Next, the present invention will be described by way of examples. The present invention is not limited thereby. In the present examples, the reactions and treatments were carried out at room temperature (23 °C) and atmospheric pressure unless otherwise specified. Also, amounts, parts, %, etc. are on a mass basis unless otherwise specified.

[0072] (Method for preparing a two - component addition - curable composition kit) As shown in the following table, the first liquid and the second liquid of the two - component addition - curable composition kit were prepared. As an example of preparation, Example 1 is described below. The other examples and comparative examples were prepared in the same manner.

[0073] (Example 1) First liquid: First, 50.0 parts by mass of polydimethylsiloxane containing alkenyl groups only at the molecular chain ends, which is blocked at both ends with dimethylvinylsilyl groups and has a viscosity of 1000 mPa·s, as component (A); 0.09 parts by mass of 1 - ethynyl - 1 - cyclohexanol (manufactured by Nisshin Chemical Industry Co., Ltd.) as component (C); 0.35 parts by mass of a platinum - vinylsiloxane complex solution (platinum content: 100 ppm / g) as component (D); 1.0 part by mass of an alkenyl - group - containing polydimethylsiloxane having a viscosity of 600 mPa·s and containing alkenyl groups at both ends and side chains (alkenyl - group content: 1.7 mmol / g) as component (E); 0.1 part by mass of sorbic acid as a preservative; and 6.5 parts by mass of a nonionic surfactant (Pegnol T10 / 80 manufactured by Toho Chemical Industry Co., Ltd.) as component (F) were added and mixed. Further, purified water as component (G) was added so that the total mass of the first liquid became 100 parts by mass, and the first liquid was prepared by stirring at 4000 rpm using an IKA Ultra Turrax T50 basic shaft generator G45M. Regarding the platinum content, it was formulated so that [(alkenyl groups (mol) in component (E) / platinum atoms (mol))] became 104. Through the above steps, silicone emulsion (I) was prepared.

[0074] Second Liquid: First, 35.0 parts by mass of methylhydrogenpolysiloxane having an SiH group in the side chain and a viscosity of 40 mPa·s (25°C) with both ends of the molecular chain blocked by trimethylsiloxy groups as component (B), 5.0 parts by mass of a nonionic surfactant (Pegnol T10 / 80 manufactured by Toho Chemical Industry Co., Ltd.) as component (F), 59.9 parts by mass of purified water as component (G), and acetic acid as a pH adjuster were stirred at 4000 rpm using an IKA Ultra Turrax T50 basic shaft generator G45M to prepare silicone emulsion (II).

[0075] The mixing ratio of the first liquid and the second liquid was mixed so that the hydrogen-alkenyl ratio (NH / NA) was 2.0. Specifically, 6.4 parts of the second liquid was mixed with 100 parts of the first liquid at a mixing ratio while stirring with a weighing magnetic stirrer.

[0076] (Example 2) First Liquid: The same as silicone emulsion (I) in Example 1 Second Liquid: The same as silicone emulsion (II) in Example 1 The mixing ratio of the first liquid and the second liquid was mixed so that the hydrogen-alkenyl ratio (NH / NA) was 1.5. Specifically, the mixing ratio of the second liquid was 4.8 parts with respect to 100 parts of the first liquid.

[0077] (Example 3) First Liquid: The same as silicone emulsion (I) in Example 1 Second Liquid: The same as silicone emulsion (II) in Example 1 The mixing ratio of the first liquid and the second liquid was mixed so that the hydrogen-alkenyl ratio (NH / NA) was 2.5. Specifically, the mixing ratio of the second liquid was 8.0 parts with respect to 100 parts of the first liquid.

[0078] (Example 4) First Liquid: 0.7 part of alkenyl group-containing polydimethylsiloxane (alkenyl group content: 2.8 mmol / g) with a viscosity of 1000 mPa·s and having alkenyl groups at both ends and side chains as component (E) was used, component (D) was blended such that [(alkenyl groups (mol) in component (E)) / (platinum atoms (mol))] = 120, and further the amount of purified water as component (G) was adjusted so that the total amount of components of the first liquid became 100 parts by mass. The first liquid was prepared by blending in the same manner as in Example 1 except for these matters. Second Liquid: The same as the silicone emulsion (I) of Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) became 2.0.

[0079] (Example 5) First Liquid: The same as in Example 4 Second Liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) became 1.5.

[0080] (Example 6) First Liquid: The same as in Example 4 Second Liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) became 2.5.

[0081] (Example 7) First Liquid: The first liquid was prepared by blending in the same manner as in Example 1 except that 0.09 part by mass of 3,5-dimethyl-1-hexyne-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as component (C). Second Liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) became 2.0.

[0082] (Example 8) First Liquid: The same as in Example 7 Second Liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) became 1.5.

[0083] (Example 9) First liquid: The same as in Example 7 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.5.

[0084] (Example 10) First liquid: The first liquid was prepared in the same manner as in Example 1, except that 0.09 parts by mass of 4-ethyl-1-octyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as component (C). Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0085] (Example 11) First liquid: The same as in Example 10 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 1.5.

[0086] (Example 12) First liquid: The same as in Example 10 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.5.

[0087] (Example 13) First liquid: 2.0 parts of an alkenyl group-containing polydimethylsiloxane having an alkenyl group at both ends and side chains and a viscosity of 600 mPa·s (alkenyl group content: 1.7 mmol / g) was used as component (E), and component (D) was blended so that the platinum content was [(alkenyl group (mol) in component (E) / platinum atom (mol))] = 209. Further, the amount of purified water as (G) was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was prepared by blending in the same manner as in Example 1, except for these matters. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0088] (Example 14) First liquid: The same as in Example 13 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 1.5.

[0089] (Example 15) First liquid: The same as in Example 13 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.5.

[0090] (Example 16) First liquid: 0.8 part of an alkenyl group-containing polydimethylsiloxane having an alkenyl group at both ends and side chains, a viscosity of 600 mPa·s, and an alkenyl group content of 1.7 mmol / g was used as the (E) component, and the (D) component was blended so that the platinum content was [(alkenyl group (mol) in the (E) component / platinum atom (mol)] = 84. Further, the amount of purified water as the (G) component was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was prepared by blending in the same manner as in Example 1 except for these matters. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0091] (Example 17) First liquid: The same as in Example 16 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 1.5.

[0092] (Example 18) First liquid: The same as in Example 16 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.5.

[0093] (Example 19) First liquid: As component (A), 25.0 parts by mass each of alkenyl group-containing polydimethylsiloxanes having viscosities of 1,000 mPa·s and 20,000 mPa·s, each blocked at both ends with dimethylvinylsilyl groups, were used. Except for this item, the first liquid was prepared by mixing in the same manner as in Example 1. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0094] (Example 20) First liquid: The same as in Example 19 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 1.5.

[0095] (Example 21) First liquid: The same as in Example 19 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.5.

[0096] (Example 22) First liquid: As component (A), 41.0 parts by mass of an alkenyl group-containing polydimethylsiloxane having a viscosity of 1,000 mPa·s and blocked at both ends with dimethylvinylsilyl groups was used. As component (E), 9.0 parts of an alkenyl group-containing polydimethylsiloxane having a viscosity of 600 mPa·s and containing alkenyl groups at both ends and in the side chains (alkenyl group content: 1.7 mmol / g) was used. Component (D) was blended so that [(alkenyl groups (mol) in component (E)) / (platinum atoms (mol))] = 940. Further, the amount of purified water as component (G) was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. Except for these items, the first liquid was prepared by mixing in the same manner as in Example 1. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0097] (Example 23) First liquid: The same as in Example 22 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 1.5.

[0098] (Example 24) First liquid: The same as in Example 22 Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.5.

[0099] (Comparative Example 1) First liquid: The (E) component was not blended, and the amount of purified water as the (G) component was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The blending was carried out in the same manner as in Example 1 except for these matters. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0100] (Comparative Example 2) First liquid: 0.2 part of an alkenyl group-containing polydimethylsiloxane having an alkenyl group at both ends and side chains and a viscosity of 1000 mPa·s (alkenyl group content: 2.8 mmol / g) was used as the (E) component, and the (D) component was blended so that [(alkenyl group (mol) in the (E) component / platinum atom (mol))] = 20, and further, the amount of purified water as the (G) component was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was adjusted by blending in the same manner as in Example 1 except for these matters. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0101] (Comparative Example 3) First liquid: The (C) component was not blended, and the amount of purified water as the (G) component was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was adjusted by blending in the same manner as in Example 1 except for these matters. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0102] (Comparative Example 4) First liquid: The (C) component was not blended, and the amount of purified water as the (G) component was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was adjusted by blending in the same manner as in Example 1 except for these matters. Second liquid: 0.09 part by mass of 1-ethynyl-1-cyclohexanol (manufactured by Nisshin Chemical Industry Co., Ltd.) was used as the (C) component, and the amount of purified water as the (G) component was adjusted so that the total amount of the components of the second liquid was 100 parts by mass. The second liquid was adjusted by blending in the same manner as in Example 1 except for these matters. The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0103] (Comparative Example 5) First liquid: The same as in Comparative Example 4 Second liquid: The same as in Comparative Example 4 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 12.8. In other words, the mixing was carried out so that the ratio of the platinum catalyst of the (D) component and the inhibitor of the (C) component in the two-liquid mixture was the same as in Example 1.

[0104] (Comparative Example 6) First Liquid: 40.0 parts by mass of an alkenyl group-containing polydimethylsiloxane with a viscosity of 1,000 mPa·s and both ends blocked with dimethylvinylsilyl groups was used as component (A). 10.0 parts of an alkenyl group-containing polydimethylsiloxane with a viscosity of 20,000 mPa·s and containing alkenyl groups at both ends and in the side chains (alkenyl group content: 0.24 mmol / g) was used as component (E). Component (D) was blended so that [(alkenyl groups (mol) in component (E)) / (platinum atoms (mol))] = 147. Further, the amount of purified water as component (G) was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was prepared by blending in the same manner as in Example 1 except for these matters. Second Liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0105] (Comparative Example 7) First Liquid: For comparison, instead of component (E), 0.2 part of 1,3-divinyltetramethyldisiloxane with a viscosity of ~1.0 mPa·s and containing alkenyl groups at both ends (alkenyl group content: 10.7 mmol / g) was used. Component (D) was blended so that [(alkenyl groups (mol) in 1,3-divinyltetramethyldisiloxane component) / (platinum atoms (mol))] = 131. Further, the amount of purified water as component (G) was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was prepared by blending in the same manner as in Example 1 except for these matters. Second Liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0106] (Comparative Example 8) First Liquid: 0.09 part by mass of 3,5-dimethyl-1-hexyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as component (C). Component (E) was not blended. Further, the amount of purified water as component (G) was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was prepared by blending in the same manner as in Example 1 except for these matters. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0107] (Comparative Example 9) First liquid: 0.09 parts by mass of 4-ethyl-1-octyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C), the component (E) was not blended, and further, the amount of purified water as the component (G) was adjusted so that the total amount of the components of the first liquid was 100 parts by mass. The first liquid was prepared by blending in the same manner as in Example 1 except for these matters. Second liquid: The same as in Example 1 The mixing ratio of the first liquid and the second liquid was adjusted so that the hydrogen-alkenyl ratio (NH / NA) was 2.0.

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3]

[0111] [Table 4]

[0112] (Evaluation method) (Judgment of curing speed) The two-component addition-curable composition adjusted and mixed by the above method was applied to one side of ESTER G2C (thickness: 50 μm) manufactured by Toyobo Co., Ltd. and dried by heating in an oven at 150°C. The time required for the curing of the coated surface to be completed was measured, and criteria were set as follows for this curing time (curing speed) and evaluated. Pass was defined as B or above. A: Less than 30 seconds B: 30 seconds or more and less than 60 seconds C: More than 60 seconds and less than 120 seconds D: 120 seconds or more E: Unable to measure (not cured, etc.)

[0113] <Curing completion criterion> In the determination of the above curing rate, the completion of curing was determined as follows. By strongly rubbing the surface of the peeled film after curing 5 times with a finger, if the coated surface becomes white and cloudy (a state called smearing), it was judged that the curing was insufficient and uncured. If no change was seen on the rubbed coated surface, it was judged that there was no curing problem and curing was completed.

[0114] <Method for producing a release film> The two-component addition-curable composition adjusted and mixed by the above method was applied to one side of Ester G2C (thickness 50 μm) manufactured by Toyobo Co., Ltd. using a Mayer bar coater No. 3. A release film sample was prepared by heating and curing at 150 °C in an oven for 2 minutes.

[0115] <Method for measuring peel force> After holding the release film produced by the above method at room temperature for 30 minutes or more, TESA7475 (tape for confirming silicone coating performance, manufactured by Tesafilm Co., Ltd.) was bonded to the coated surface, crimped with a roller, and a weight of 20 g / cm 2 was placed on it, and this state was maintained at 40 °C for 20 hours. Then, the peel force when the tape was peeled off from the film was measured at a peel angle of 180° and a peel speed of 0.3 m / min (FINAT Test Method No. 10 (refer to FINAT Technical Handbook 9 th edition, 2014).

[0116] <Method for measuring residual adhesion rate> A polyester adhesive tape Nittoh No. 31B (manufactured by Nitto Denko Corporation) was bonded to the coated surface of the release film produced as described above, crimped with a roller, and 20 g / cm 2Weighed down and maintained this state at 40 °C for 20 hours to perform aging. After aging, the adhesive tape peeled off from the release film was pressure-bonded to a stainless steel plate with a roller, and then the peel strength of the adhesive tape was measured at a peel angle of 180° and a peel speed of 0.3 m / min. The value of the peel strength at that time was taken as the peel strength with respect to the stainless steel plate after being bonded to the release film. Also, polyester adhesive tape Nitto No. 31B (manufactured by Nitto Denko Corporation) was pressure-bonded to a stainless steel plate with a roller, and then the peel strength of the adhesive tape was measured at a peel angle of 180° and a peel speed of 0.3 m / min. The value of this peel strength was taken as the peel strength with respect to the stainless steel plate of the blank (without bonding to the release film of the present invention). The value calculated by the following formula was taken as the residual adhesion rate (%). Residual adhesion rate (%) = (Peel strength with respect to the stainless steel plate after bonding to the release film) / (Peel strength with respect to the stainless steel plate of the blank) × 100

[0117] <Visual evaluation of the appearance (discoloration) of the composition> In a two-component addition-curable composition, in many cases where appearance abnormalities occur, it is in the first liquid containing a platinum catalyst. When appearance abnormalities occur in the first liquid, appearance abnormalities also occur in the cured product obtained by curing the two-component addition-curable composition using this. Therefore, the degree of appearance (discoloration) of the first liquid was evaluated. Regarding the first liquid, after mixing the components (A), (C), (D), and (E), it was left standing for 1 day, and it was visually judged whether the color tone of the composition had changed, and evaluation was carried out by setting the following criteria. Pass was defined as B or above. A: Transparent (no change) B: Light yellow C: Dark yellow to brown D: Black

[0118] <Visual evaluation of the cured product> Regarding the two - component addition - curable composition, a release film (a cured film which is the cured product of the two - component addition - curable composition of the present invention) was prepared according to the above - mentioned method for producing a release film, and the appearance was visually confirmed. When the appearance of the cured film was colorless and transparent, there was no abnormality. When the cured film was colored and changed color to yellow, brown, black, etc., it was regarded as abnormal. In the case where it did not cure, the evaluation of the cured product was not carried out, and it was evaluated as non - viable (described as "-" in the table).

[0119] <Evaluation of pot life> The working time (pot life) after mixing the first liquid and the second liquid was evaluated. After mixing the first liquid and the second liquid of the two - component addition - curable composition at room temperature, it was put into a plastic container, covered, and the presence or absence of solid matter generation on the liquid surface was visually observed. The time until solid matter (usually in a gel state) was generated in the composition was defined as the working time, and evaluation was carried out by setting the following criteria. Pass was defined as B or above. A: 1 day or more B: half a day or more C: more than 1 hour and less than half a day D: less than 1 hour

[0120] (Results) As is clear from the results shown in the table, the results of Examples 1 - 24 were evaluated as B or above in all of the curability evaluation, appearance evaluation, and pot life evaluation, and excellent results were obtained. Moreover, for the composition of the present invention, even when the mixing ratio of the first liquid and the second liquid was changed to vary the ratio of alkenyl organopolysiloxane and organohydrogenpolysiloxane, the curing rate could be maintained at the desired level, and it could be used without affecting workability such as pot life. Also, no abnormality in appearance was observed, and it was confirmed that it was possible to change the desired curing characteristics.

[0121] When formulated so that the hydrogen - alkenyl ratio (NH / NA) was in the range of 1.3 ≦ (NH / NA) ≦ 4.0, it was confirmed that the residual adhesion rate was all 85% or more, and it was a good cured film with little transferability to the object to be peeled as a release agent.

[0122] When the component (E) was not added as in Comparative Examples 1, 7, 8, and 9, appearance abnormalities were observed in all cases. The component (E) is considered to have a function of reducing the stability of the platinum complex of the component (D) and the strong interaction with the inhibitor of the component (C), and the result supports that it is an essential component in the composition of the present invention.

[0123] Also, when inhibitors having different structures were used as the component (C) (Examples 4 to 6), it was confirmed that the component (E) could coordinate well with the platinum catalyst of the component (D) and exhibit the effect of suppressing appearance abnormalities. On the other hand, appearance abnormalities were also observed when the (E) component having an alkenyl group content outside a predetermined range (Comparative Example 6), viscosity (Comparative Example 7), or when the blending amount of the (E) component did not satisfy the predetermined range (Comparative Example 2).

[0124] In Comparative Example 3 where the inhibitor of the component (C) was not added and Comparative Example 4 where the inhibitor of the component (C) was added to the second liquid, although appearance abnormalities were not observed, the pot life was significantly reduced. Even when the inhibitor of the component (C) was added to the second liquid, it was possible to adjust the amount of the inhibitor of the component (C) with respect to the platinum catalyst of the component (D) by adjusting the addition amount of the second liquid as in Comparative Example 5, but it was impossible to freely change the mixing ratio of the first liquid and the second liquid. Also, as a result of adding an excessive amount of the second liquid, the peelability properties also changed significantly (Comparative Examples 4 and 5).

Industrial Applicability

[0125] The two-component addition-curable composition kit of the present invention functions suitably as a peelable material that can maintain a constant curing rate and pot life even when the user changes the mixing ratio of the first liquid and the second liquid. By forming a cured film obtained by curing the two-component addition-curable composition on the surface of a thin-layer substrate such as paper and plastic, it is possible to adhere well to these substrates and provide a release paper, a release film, and the like.

Claims

1. A two-part addition curable composition kit comprising a first liquid and a second liquid, The first liquid is Component (A): an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less; (C) component: an inhibitor; (D) component: a platinum catalyst; Component (E): an organopolysiloxane having at least one alkenyl group bonded to a silicon atom in a side chain of the molecular chain, with an alkenyl group content per molecule of 1.7 mmol / g or more and a viscosity at 25°C of 100 mPa·s or more and 100,000 mPa·s or less; Including, The first liquid does not contain organohydrogenpolysiloxane, the amount of the component (E) blended in the first liquid is an amount such that the molar ratio of alkenyl groups in the component (E) to platinum atoms [alkenyl groups in the component (E) / platinum] is 50 or more and 1,000 or less; The second liquid is (B) Component: An organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in each molecule, the second liquid does not contain the component (A), the component (C), the component (D), or the component (E); An addition curable composition can be obtained by mixing the first liquid and the second liquid. A two-part addition curable composition kit comprising:

2. The component (C) is an alkynol compound, The component (D) is a platinum-vinylsiloxane complex.

2. The two-part addition curable composition kit according to claim 1 .

3. The first liquid further comprises a preservative; The second liquid further contains a pH adjuster.

2. The two-part addition curable composition kit according to claim 1 .

4. 13. A two-part addition curable composition kit according to claim 1 for producing a peelable material.

5. A substrate; A cured coating formed on a substrate by curing the addition curable composition according to any one of claims 1 to 4; A peelable material comprising:

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