Method for producing an organopolysiloxane cured product, organopolysiloxane cured product, laminate, and optical component

Abstract

[Problem] To provide a cured product using a composition that can be rapidly cured at low temperatures while having a sufficient pot life at room temperature, a method for producing the same, a laminate in which the cured product is disposed between layers, and an optical device in which the cured product is used as an optical component. [Solution] A method for producing a cured organopolysiloxane product, comprising: step (i): subjecting a composition containing a first hydrosilylation catalyst that is active in the composition without high-energy radiation and a second hydrosilylation catalyst that is inactive in the absence of high-energy radiation but becomes active in the composition upon high-energy radiation to a hydrosilylation reaction without high-energy radiation to obtain a thickened product that is fluid at room temperature or a thermoplastic that is non-fluid at room temperature but fluid at 100°C; and step (ii): irradiating the thickened product or thermoplastic obtained in step (i) with high-energy radiation to obtain a cured product.

Description

Technical Field

[0001] The present invention relates to an organopolysiloxane cured product produced by a two-step hydrosilylation reaction, a method for producing the same, a laminate in which the cured product is disposed between layers, a method for producing the same, and an optical device using the cured product.

Background Art

[0002] Silicone materials obtained from organopolysiloxanes have excellent properties such as heat resistance, chemical resistance, and electrical insulation, and are thus used in various applications. Silicone materials can be formed on various substrates such as plastics, metals, glasses, ceramics, papers, and woods, and the applications also cover a wide range, including daily necessities, medical supplies, and electronic products. In recent years, silicone materials have been widely used as transparent members that require heat resistance and light resistance in laminates such as image display devices and optical devices such as lighting devices. Silicone materials are usually obtained by crosslinking organopolysiloxanes by a hydrosilylation reaction. In the hydrosilylation reaction, a transition metal complex catalyst that is usually activated by heat is used from the viewpoint of workability and the like. In order to achieve curing of organopolysiloxanes in a short time, it is necessary to heat to a high temperature. However, when forming a silicone material on a substrate such as a thermoplastic resin film, since the substrate cannot be heated to a high temperature, a catalyst activated by irradiation with high energy rays such as ultraviolet rays is used (Patent Document 1).

[0003] However, an organopolysiloxane composition using a high energy ray-activated catalyst does not cure immediately even when irradiated with high energy rays, and in many cases, heating is required to cure it in a short time. When the amount of the catalyst is increased so as to cure in a short time, there is a problem that the cured product is colored. Further, when curing is performed at a low temperature with a low catalyst amount, the curing reaction is not completed, resulting in a cured product having low mechanical strength.

[0004] On the one hand, in order to complete curing at a low temperature in a short time using a catalyst activated by heat, it is necessary to increase the amount of the catalyst. In addition to the problem that the cured product is colored, there is also a problem that the viscosity increases very rapidly and the pot life at room temperature becomes short. Furthermore, when curing at a low temperature with a low amount of catalyst, there is a problem that the curing reaction is not completed, resulting in a cured product with low mechanical strength.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, an object of the present invention is to provide a cured product using a composition that can be cured at a high speed at a low temperature while having a sufficient pot life at room temperature, a method for producing the same, a laminate in which these cured products are arranged between layers, and an optical device in which these cured products are used as optical members.

Means for Solving the Problems

[0007] The method for producing an organopolysiloxane cured product of the present invention includes step (i): performing a hydrosilylation reaction on a composition containing components (A) to (D) described later without irradiation with high-energy rays to obtain a thickener having fluidity at room temperature or a thermoplastic that is non-fluid at room temperature but shows fluidity at 100°C, and step (ii): irradiating the thickener or thermoplastic obtained in the above step (i) with high-energy rays. The components (A) to (D) are as follows.

[0008] (A) The following average composition formula (1): R 1 a R 2 b SiO (4-a―b) / 2 (1) (In the formula, R 1is an alkenyl group having 2 to 12 carbon atoms, R 2 is a group selected from monovalent hydrocarbon groups having 1 to 12 carbon atoms, hydroxyl groups, and alkoxy groups that do not have aliphatic unsaturated bonds, and a and b are numbers that satisfy the following conditions: 1 ≦ a + b ≦ 3 and 0.001 ≦ a / (a + b) ≦ 0.33) represented by an organopolysiloxane, (B) The following average composition formula (2): H c R 3 d SiO (4-c-d) / 2 (2) (In the formula, R 3 is a group selected from monovalent hydrocarbon groups having 1 to 12 carbon atoms, hydroxyl groups, and alkoxy groups that do not have aliphatic unsaturated bonds, and c and d are numbers that satisfy the following conditions: 1 ≦ c + d ≦ 3 and 0.01 ≦ c / (c + d) ≦ 0.33) represented by an organopolysiloxane, (C) A first hydrosilylation reaction catalyst that exhibits activity in the present composition without irradiation with high-energy rays, (D) A second hydrosilylation reaction catalyst that does not exhibit activity without irradiation with high-energy rays but exhibits activity in the present composition upon irradiation with high-energy rays.

[0009] The high-energy ray is preferably any one selected from ultraviolet rays, X-rays, or electron beams. Further, the component (B) has the following average unit formula (3): (HR 4 2SiO 1 / 2 ) e (R 4 3SiO 1 / 2 ) f (HR 4 SiO 2 / 2 ) g (R 4 2SiO 2 / 2 ) h (HSiO 3 / 2 ) i (R 4 SiO 3 / 2 ) j (SiO 4 / 2 ) k (R 5 O 1 / 2 ) l (3) (wherein, each R 4 is independently a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group, and R 5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and e, f, g, h, i, j, k, and l satisfy the following conditions: e + f + g + h + i + j + k = 1, 0 ≦ l ≦ 0.1, 0.01 ≦ e + g + i ≦ 0.2, 0 ≦ e ≦ 0.6, 0 ≦ g ≦ 0.6, 0 ≦ i ≦ 0.4, 0.01 ≦ e + f ≦ 0.8, 0.01 ≦ g + h ≦ 0.8, 0 ≦ i + j ≦ 0.6) Preferably, it is an organohydrogenpolysiloxane represented by the formula. Further, the molar ratio ((C) / (D)) of the component (C) to the component (D) is preferably 0.001 to 1000.

[0010] Another aspect of the present invention relates to a cured organopolysiloxane produced by the above method.

[0011] Furthermore, another aspect of the present invention is a laminate in which a cured organopolysiloxane produced by the above method is disposed between layers, and the laminate is preferably an image display device.

[0012] Also, another aspect of the present invention relates to an optical device having a cured organopolysiloxane produced by the above method.

[0013] Furthermore, another aspect of the present invention is a method for manufacturing a laminate in which an organopolysiloxane cured product is disposed between layers, and includes the following three methods. The first method includes step (iii): applying a composition containing the components (A) to (D) onto a substrate, performing a hydrosilylation reaction without irradiation with high-energy rays, and forming a thickener having fluidity at room temperature or a thermoplastic that is non-fluid at room temperature but shows fluidity at 100°C; step (iv): forming an upper layer member on the thickener or thermoplastic layer obtained in the above step (iii); and step (v): irradiating the thickener or thermoplastic layer with high-energy rays from at least one of under the substrate, on the upper layer member, or the side surface of the thickener or thermoplastic layer.

[0014] The second method for manufacturing a laminate in which an organopolysiloxane cured product is disposed between layers includes step (vi): applying a composition containing the components (A) to (D) onto a substrate, performing a hydrosilylation reaction without irradiation with high-energy rays, and forming a thickener having fluidity at room temperature or a thermoplastic that is non-fluid at room temperature but shows fluidity at 100°C; step (vii): irradiating the thickener or thermoplastic layer obtained in the above step (vi) with high-energy rays; step (viii): forming an upper layer member on the thickener or thermoplastic layer irradiated with the high-energy rays; and step (ix): curing the thickener or thermoplastic layer by heating or leaving it at room temperature.

[0015] The third method for manufacturing a laminate in which an organopolysiloxane cured product is disposed between layers includes step (x): applying a composition containing the components (A) to (D) onto a substrate, performing a hydrosilylation reaction without irradiation with high-energy rays, and forming a thickener having fluidity at room temperature or a thermoplastic that is non-fluid at room temperature but exhibits fluidity at 100°C; step (xi): irradiating the thickener or thermoplastic layer obtained in the above step (x) with high-energy rays; step (xii): forming an upper layer member on the thickener or thermoplastic layer irradiated with the high-energy rays; and step (xiii): irradiating the thickener or thermoplastic layer with high-energy rays from at least one of the bottom of the substrate, on the upper layer member, or the side surface of the thickener or thermoplastic layer.

[0016] Another aspect of the invention of the present invention relates to a laminate obtained by any of the above methods.

[0017] Furthermore, another aspect of the invention of the present invention is a method for forming an optical device having an organopolysiloxane cured product formed on its surface, including step (ixv): applying a composition containing the components (A) to (D) onto a release film, performing a hydrosilylation reaction without irradiation with high-energy rays, and forming a thermoplastic film that is non-fluid at room temperature but exhibits fluidity at 100°C; step (xv): installing the thermoplastic film on an optical device and heating it; and step (xvi): irradiating the thermoplastic film obtained in the above step (XV) or its melt with high-energy rays.

[0018] Furthermore, another aspect of the invention of the present invention relates to an optical device obtained by the above method.

Advantages of the Invention

[0019] According to the method for producing an organopolysiloxane cured product of the present invention, since an organopolysiloxane composition containing two types of hydrosilylation catalysts that exhibit generation without irradiation of high-energy rays and a high-energy ray-activated hydrosilylation catalyst is used, low-temperature curing is easy. Further, the laminate and the optical device of the present invention can be efficiently produced in a short time, and the obtained laminate and optical device have high reliability.

Embodiments for Carrying Out the Invention

[0020] (Composition) The organopolysiloxane cured product used in the present invention is prepared from a composition containing the following components (A) to (D). They will be described in order below.

[0021] (Component (A)) Component (A) is a compound containing an aliphatic unsaturated group to which a hydrosilyl group (—SiH) adds during the hydrosilylation reaction, and is an organopolysiloxane having the following average composition formula (1).

[0022] R 1 a R 2 b SiO (4-a―b) / 2 (1)

[0023] In the general formula (1), R 1 is an alkenyl group having 2 to 12 carbon atoms. Specifically, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group can be mentioned, and among these, vinyl group, allyl group or hexenyl group is preferable. R 2is a group selected from monovalent hydrocarbon groups having 1 to 12 carbon atoms without aliphatic unsaturated bonds, hydroxyl groups, and alkoxy groups. In the monovalent hydrocarbon group having 1 to 12 carbon atoms, a part of its hydrogen atoms may be substituted with a halogen atom or a hydroxyl group. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group; aralkyl groups such as benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group, phenanthrylethyl group, pyrenylethyl group; and groups in which the hydrogen atoms of these aryl groups or aralkyl groups are substituted with alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group; and halogen atoms such as chlorine atom and bromine atom.

[0024] a and b are numbers satisfying the following conditions: 1 ≤ a + b ≤ 3 and 0.001 ≤ a / (a + b) ≤ 0.33, and preferably numbers satisfying the following conditions: 1.5 ≤ a + b ≤ 2.5 and 0.005 ≤ a / (a + b) ≤ 0.2. This is because when a + b is not less than the lower limit of the above range, the flexibility of the cured product becomes high, while when it is not more than the upper limit of the above range, the mechanical strength of the cured product becomes high. When a / (a + b) is not less than the lower limit of the above range, the mechanical strength of the cured product becomes high, while when it is not more than the upper limit of the above range, the flexibility of the cured product becomes high.

[0025] Examples of the molecular structure of such organopolysiloxane include linear, branched, or cyclic structures. The organopolysiloxane may be a mixture of one or more compounds having such molecular structures.

[0026] Examples of such component (A) include the general formula: R 6 3SiO(R 6 2SiO) t SiR 6 3 A linear organopolysiloxane represented by and / or an average unit formula: (R 6 SiO 3 / 2 ) o (R 6 2SiO 2 / 2 ) p (R 6 SiO 1 / 2 ) q (SiO 4 / 2 ) r (XO 1 / 2 ) s A branched-chain organopolysiloxane represented by is preferred. In the formula, each R 6 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and the same groups as described above are exemplified. X is a hydrogen atom or an alkyl group. However, in one molecule, at least 2 R 6 are alkenyl groups. As this alkenyl group, a vinyl group is preferred. Further, since the attenuation of the obtained cured product due to light refraction, reflection, scattering, etc. is small, at least 30 mol% of all R 6 in one molecule are aryl groups, preferably at least 40 mol% are aryl groups. As this aryl group, a phenyl group is preferred. Also, in the formula, t is an integer in the range of 5 to 1,000. Also, in the formula, o is a positive number, p is 0 or a positive number, q is 0 or a positive number, r is 0 or a positive number, s is 0 or a positive number, and p / o is a number in the range of 0 to 10, q / o is a number in the range of 0 to 5, r / (o + p + q + r) is a number in the range of 0 to 0.3, and s / (o + p + q + r) is a number in the range of 0 to 0.4.

[0027] On the other hand, the component (A) may be (a1) a linear or branched-chain organopolysiloxane having an alkenyl group with 2 to 12 carbon atoms at the molecular chain ends, (a2) an average unit formula: (R 5 3SiO 1 / 2 ) m (R 5 2SiO 2 / 2 ) n (R 5 SiO 3 / 2 )o (SiO 4 / 2 ) p (wherein R 5 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and m, n, o, and p are subject to the following conditions: m + n + o + p = 1, 0.2 ≤ m ≤ 0.5, 0 ≤ n ≤ 0.3, 0 ≤ o ≤ 0.8, 0 ≤ p ≤ 0.6, 0.2 ≤ o + p ≤ 0.8) It may be an organopolysiloxane resin represented by It may also be a mixture of the above components (a1) and (a2). In particular, by using such a mixture together with the component (B), a thermoplastic having heat-melting properties can be obtained.

[0028] Component (B) Component (B) is a compound containing a hydrosilyl group (—SiH) that adds to the alkenyl group in the component (A) during the hydrosilylation reaction, and is an organopolysiloxane having the following average composition formula (2).

[0029] H c R 3 d SiO (4-c-d) / 2 (2)

[0030] In the general formula (2), R 3is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group. In the monovalent hydrocarbon group having 1 to 12 carbon atoms, a part of its hydrogen atoms may be substituted with a halogen atom or a hydroxyl group. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group; aralkyl groups such as benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group, phenanthrylethyl group, pyrenylethyl group; and groups in which the hydrogen atoms of these aryl groups or aralkyl groups are substituted with an alkyl group such as methyl group and ethyl group; an alkoxy group such as methoxy group and ethoxy group; a halogen atom such as chlorine atom and bromine atom. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentanoxy group, hexanoxy group, octanoxy group, etc.

[0031] c and d are numbers satisfying the following conditions: 1 ≦ c + d ≦ 3 and 0.01 ≦ c / (c + d) ≦ 0.33, and preferably, numbers satisfying the following conditions: 1.5 ≦ c + d ≦ 2.5 and 0.05 ≦ c / (c + d) ≦ 0.2. This is because when c + d is above the lower limit of the above range, the flexibility of the cured product becomes high, while when it is below the upper limit of the above range, the mechanical strength of the cured product becomes high. When c / (c + d) is above the lower limit of the above range, the mechanical strength of the cured product becomes high, while when it is below the upper limit of the above range, the flexibility of the cured product becomes high.

[0032] The viscosity of the organopolysiloxane having the average composition formula (2) is not limited, but preferably the viscosity at 25°C is in the range of 0.5 to 10,000 mPa·s, and particularly preferably in the range of 1 to 1,000 mPa·s.

[0033] Examples of the organopolysiloxane having the average composition formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, methylhydrogenpolysiloxane blocked at both ends of the molecular chain with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer blocked at both ends of the molecular chain with trimethylsiloxy groups, dimethylpolysiloxane blocked at both ends of the molecular chain with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer blocked at both ends of the molecular chain with dimethylhydrogensiloxy groups, methylhydrogenpolysiloxane-diphenylsiloxane copolymer blocked at both ends of the molecular chain with trimethylsiloxy groups, methylhydrogenpolysiloxane-diphenylsiloxane-dimethylsiloxane copolymer blocked at both ends of the molecular chain with trimethylsiloxy groups, hydrolysis condensate of trimethoxysilane, copolymer composed of (CH3)2HSiO 1 / 2 units and SiO 4 / 2 units, copolymer composed of (CH3)2HSiO 1 / 2 units and SiO 4 / 2 units and (C6H5)SiO 3 / 2 units, and mixtures of two or more of these are exemplified.

[0034] Examples of the organopolysiloxane having the average composition formula (2) further include the following organopolysiloxanes. In the formula, Me and Ph represent a methyl group and a phenyl group, respectively, m1 is an integer of 1 to 100, n1 is an integer of 1 to 50, and b1, c1, d1, and e1 are positive numbers, provided that the sum of b1, c1, d1, and e1 in one molecule is 1. HMe2SiO(Ph2SiO) m1 SiMe2H HMePhSiO(Ph2SiO) m1 SiMePhH HMePhSiO(Ph2SiO) m1 (MePhSiO) n1 SiMePhH HMePhSiO(Ph2SiO)m1 (Me2SiO) n1 SiMePhH (HMe2SiO 1 / 2 ) b1 (PhSiO 3 / 2 ) c1 (HMePhSiO 1 / 2 ) b1 (PhSiO 3 / 2 ) c1 (HMePhSiO 1 / 2 ) b1 (HMe2SiO 1 / 2 ) c1 (PhSiO 3 / 2 ) d1 (HMe2SiO 1 / 2 ) b1 (Ph2SiO 2 / 2 ) c1 (PhSiO 3 / 2 ) d1 (HMePhSiO 1 / 2 ) b1 (Ph2SiO 2 / 2 ) c1 (PhSiO 3 / 2 ) d1 (HMePhSiO 1 / 2 ) b1 (HMe2SiO 1 / 2 ) c1 (Ph2SiO 2 / 2 ) d1 (PhSiO 3 / 2 ) e1

[0035] Component (B) is preferably an organohydrogenpolysiloxane represented by the following average unit formula (3).

[0036] (HR 4 2SiO 1 / 2 ) e (R 4 3SiO 1 / 2 ) f (HR 4 SiO 2 / 2 ) g (R 4 2SiO2 / 2 ) h (HSiO 3 / 2 ) i (R 4 SiO 3 / 2 ) j (SiO 4 / 2 ) k (R 5 O 1 / 2 ) l (3)

[0037] In general formula (3), each R 4 is independently a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group. The monovalent hydrocarbon group having 1 to 12 carbon atoms, the hydroxyl group, and the alkoxy group are the same as those described above. R 5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. e, f, g, h, i, j, k, and l are numbers satisfying the following conditions: e + f + g + h + i + j + k = 1, 0 ≦ l ≦ 0.1, 0.01 ≦ e + g + i ≦ 0.2, 0 ≦ e ≦ 0.6, 0 ≦ g ≦ 0.6, 0 ≦ i ≦ 0.4, 0.01 ≦ e + f ≦ 0.8, 0.01 ≦ g + h ≦ 0.8, and 0 ≦ i + j ≦ 0.6.

[0038] In addition, the above-mentioned "HR 4 2SiO 1 / 2 ", "R 4 3SiO 1 / 2 ", "HR 4 SiO 2 / 2 ", "R 4 2SiO 2 / 2 ", "HSiO 3 / 2 ", "R 4 SiO 3 / 2 ", and "SiO 4 / 2 " structural units are units of the partial structure of organohydrogenpolysiloxane called M H unit, M unit, D H unit, D unit, T H unit, T unit, Q unit, respectively. "R 5 O 1 / 2 " is the D unit, D H unit, T unit, TH It is a group that binds to an oxygen atom in a unit or a Q unit, and means a silicon atom-bonded hydroxyl group (Si-OH) in an organopolysiloxane or a silicon atom-bonded alkoxy group remaining unreacted during the production of an organopolysiloxane. M H The M unit mainly exists at the molecular chain ends of an organohydrogenpolysiloxane, and the D H The D unit exists in the molecular chain of an organohydrogenpolysiloxane.

[0039] The content of the component (B) is an amount such that the silicon atom-bonded hydrogen atoms in this component are in the range of 0.1 to 5 moles, preferably in the range of 0.5 to 2 moles, per 1 mole of the total alkenyl groups in the component (A). This is because when the content of the component (B) is not less than the lower limit of the above range, the mechanical strength of the cured product increases, while when it is not more than the upper limit of the above range, the flexibility of the cured product increases.

[0040] In particular, in the present invention, the mixture of the component (A) and the component (B) is preferably a thermoplastic having heat-melting properties. By using such components, heat-melting properties can be imparted to the entire composition. In particular, from the viewpoint of heat-melting properties, it is particularly preferable that the component (A) is a mixture containing the above-mentioned components (a1) and (a2).

[0041] That is, the composition used in the production method of the present invention may be a thermoplastic having heat fusibility, which is non-fluid at 25°C and can have a viscosity of 1,000 Pa·s or less, preferably 500 Pa·s or less at 100°C. Here, non-fluid means not flowing in a no-load state. For example, it indicates a state below the softening point measured by the ring and ball method for the softening point of hot melt adhesives defined in JIS K 6863-1994 "Test Method for Softening Point of Hot Melt Adhesives". That is, in order to be non-fluid at 25°C, the softening point needs to be higher than 25°C. This is because when it is non-fluid at 25°C, the shape retention at that temperature is good. Also, when the melt viscosity at 100°C is within the above range, processing into various shapes becomes easy, and it can well follow the unevenness on the member in the molten state to fill the steps, and it has excellent gap filling properties. Note that this property is mainly determined by the whole composition, particularly the selection and content of the constituent components of this composition. In particular, it is a property realized by the content of the organopolysiloxane resin, which is the (a2) component in the (A) component, and the selection of the (B) component, but is not limited thereto.

[0042] (C) component Component (C) is a first hydrosilylation catalyst that exhibits activity in the present composition without irradiation with high-energy rays. Component (C) is a catalyst for the hydrosilylation reaction for semi-curing the present composition, and examples thereof include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, and preferably a platinum-based catalyst. Examples of this platinum-based catalyst include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum olefin complex, a platinum alkenylsiloxane complex, etc., and particularly a platinum alkenylsiloxane complex is preferable. Examples of this alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which a part of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups, etc. In particular, since the stability of this platinum-alkenylsiloxane complex is good, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable. Further, since the stability of this platinum-alkenylsiloxane complex can be improved, it is preferable to add an alkenylsiloxane such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as dimethylsiloxane oligomer to this complex, and particularly preferably an alkenylsiloxane is added.

[0043] (C) component catalyst is a catalyst that shows activity without irradiation of high-energy rays, and among them, those showing activity even at relatively low temperatures are preferred. Specifically, it shows activity in the composition in the temperature range of 0 to 200 °C and promotes the hydrosilylation reaction. The content of the (C) component varies depending on the type of catalyst and the type of composition, but usually, for the composition, the amount of metal atoms in this catalyst is in the range of 0.01 to 50 ppm by mass unit, preferably in the range of 0.1 to 30 ppm.

[0044] (D) component (D) component is a second hydrosilylation catalyst that does not show activity without irradiation of high-energy rays but shows activity in this composition by irradiation of high-energy rays. The (D) component is what is called a so-called high-energy ray activation catalyst or photoactivation catalyst and is known in this technical field.

[0045] Here, the high-energy rays refer to ultraviolet rays, gamma rays, X-rays, alpha rays, electron beams, etc., and ultraviolet rays, X-rays, and electron beams irradiated from a commercially available electron beam irradiation device are preferred. Industrially, ultraviolet rays in the wavelength range of 280 to 380 nm are conveniently used. Also, the irradiation amount varies depending on the type of high-energy ray-activated catalyst, but in the case of ultraviolet rays, the integrated irradiation amount at a wavelength of 365 nm is preferably in the range of 100 mJ / cm2 to 10 J / cm2.

[0046] Specific examples of component (D) include (methylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)trimethylplatinum(IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)dimethylethylplatinum(IV), (cyclopentadienyl)dimethylacetylplatinum(IV), (trimethylsilylcyclopentadienyl)trimethylplatinum(IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum(IV), (dimethylphenylsilylcyclopentadienyl)trimethylcyclopentadienylplatinum(IV), trimethyl(acetylacetonato)platinum(IV), trimethyl(3,5-heptanedionato)platinum(IV), trimethyl(methylacetoacetate)platinum(IV), bis(2,4-pentanedionato)platinum(II), bis(2,4-hexanedionato)platinum(II), bis(2,4-heptanedionato)platinum(II), bis(3,5-heptanedionato)platinum(II), bis(1-phenyl-1,3-butanedionato)platinum(II), bis(1,3-diphenyl-1,3-propanedionato)platinum(II), bis(hexafluoroacetylacetonato)platinum(II). Among these, (methylcyclopentadienyl)trimethylplatinum(IV) and bis(2,4-pentanedionato)platinum(II) are preferred in terms of versatility and ease of availability.

[0047] The content of component (D) is an amount necessary to further cure the composition semi-cured by component (C). Preferably, for this composition, the amount is such that the metal atoms in this catalyst are in the range of 1 to 50 ppm by mass, and preferably in the range of 5 to 30 ppm.

[0048] The molar ratio of component (C) to component (D) ((C) / (D)) is usually 0.001 to 1000, preferably 0.01 to 100. This is because when the molar ratio is below the upper limit, the acceleration of the curing reaction by high-energy ray irradiation can be achieved, and when the molar ratio is above the lower limit, the curing reaction can be carried out at a low temperature in a short time.

[0049] The organopolysiloxane composition used in the present invention preferably does not contain a hydrosilylation reaction inhibitor. Usually, a hydrosilylation reaction inhibitor is added to the composition in order to improve the pot life of the composition and obtain a stable composition. However, in the present invention, a stable composition can be obtained without adding a hydrosilylation reaction inhibitor, because it is preferable that the addition of the hydrosilylation reaction inhibitor does not slow down the curing reaction.

[0050] (Component (E)) Optionally, other organopolysiloxanes, adhesion promoters, inorganic fillers such as silica, glass, alumina, zinc oxide; fine powders of organic resins such as polymethacrylate resins; phosphors, heat-resistant agents, dyes, pigments, flame retardancy imparting agents, solvents, etc. are added to the organopolysiloxane composition used in the present invention. The addition amount and the method thereof are known to those skilled in the art.

[0051] The composition used in the present invention can be prepared by uniformly mixing the components (A) to (D) and, optionally, any other components. When preparing this composition, it can be mixed at room temperature using various stirrers or kneaders, and if necessary, it can also be mixed under heating. Also, there is no limitation on the order of blending of each component, and they can be mixed in any order.

[0052] The composition used in the present invention may be prepared, for example, by adding and mixing component (D) while heat-kneading components (A) to (C) in a temperature range of 80°C to 120°C. In the above temperature range, the whole composition softens and component (D) can be uniformly dispersed throughout, so there is a particular benefit in that curing defects during molding of a sheet or the like and partial cohesive failure during adhesion can be avoided. On the other hand, when the temperature is below the lower limit, softening is insufficient and it may be difficult to uniformly disperse component (D) throughout even when using mechanical force. Conversely, when the temperature exceeds the upper limit, component (D) may react during mixing and the whole may significantly thicken or cure, which is not preferable. The mixer used in this production method is not limited, and examples include single-screw or twin-screw continuous mixers, two-roll mills, Ross mixers, Hobart mixers, dental mixers, planetary mixers, kneader mixers, laboratory mills, small crushers, and Henschel mixers. Preferably, they are laboratory mills, small crushers, and Henschel mixers.

[0053] In the production of the composition used in the present invention, when the mixture of component (A) and component (B) is a thermoplastic having heat-melting properties, component (D) may be added to the melt of the thermoplastic composed of component (A), preferably component (A) containing component (a1) and component (a2), and component (B), within a range where the overall temperature is within 60°C to 140°C, preferably within 80 to 120°C, and uniformly dispersed, and then cooled. The mixer used for this dispersion operation is the same mixer as described above.

[0054] (Method for producing a cured product) The method for producing an organopolysiloxane cured product of the present invention has the following steps. (i) A step of performing a first hydrosilylation reaction on the composition containing components (A) to (D) without irradiating high-energy rays to obtain a thickened product or a thermoplastic, and (ii) A step of irradiating the obtained semi-cured product with high-energy rays and performing a second hydrosilylation reaction to obtain an organopolysiloxane cured product.

[0055] (Step (i)) Step (i) is a step of performing a first hydrosilylation reaction on the composition without irradiating high-energy rays to obtain a thickener having fluidity at room temperature or a thermoplastic that is non-fluid at room temperature but exhibits fluidity at 100°C. In this step, heating is not particularly required, but in some cases, the composition may be heated below 100°C, preferably below 60°C, to promote the first hydrosilylation reaction. The heating time depends on the types and blending amounts of the respective components in the composition, but is usually 5 minutes to 2 hours, preferably 10 minutes to 1 hour.

[0056] By step (i), a thickener having fluidity at room temperature or a thermoplastic that is non-fluid at room temperature but exhibits fluidity at 100°C is obtained. Here, the thickener means that the viscosity at 25°C is between 1.5 times and 100 times the initial viscosity of the composition. Also, the thermoplastic means that the viscosity at 100°C is 1,000,000 mPa·s or less.

[0057] (Step (ii)) Step (ii) is a step of irradiating the above-mentioned thickener or thermoplastic with high-energy rays. By irradiating with high-energy rays, the catalyst is activated, and the hydrosilylation reaction starts due to the activated catalyst. During the irradiation with high-energy rays, there are cases where the activation of the catalyst and the hydrosilylation reaction occur simultaneously, and during the irradiation with high-energy rays, mainly the activation of the catalyst occurs, and most of the hydrosilylation reaction may proceed under heating or at room temperature after the irradiation with high-energy rays. The type of high-energy rays is as described above. The irradiation amount varies depending on the type of the high-energy ray-activated catalyst, but in the case of ultraviolet rays, the integrated irradiation amount at 365 nm is preferably in the range of 100 mJ / cm2 to 10 J / cm 2 within the range.

[0058] The cases where the above-mentioned thickener or thermoplastic becomes a cured product by the above hydrosilylation reaction and the cases where, as described later, it is uncured at this point but the above-mentioned thickener or thermoplastic becomes a cured product by subsequent steps (such as heating) are included.

[0059] By step (ii) or subsequent steps, the composition that was a thickening agent or a thermoplastic becomes a cured product and can be used as various materials. Here, the cured product means that it does not flow even when heated to 200 °C or higher. The hardness of this cured product is not particularly limited, but is usually from a gel state with a penetration of 70 or less to a hard resin with a Shore D hardness of 80. Examples of subsequent steps include a heating step. When there is a heating step after step (ii), it can be heated at 0 to 200 °C, preferably 20 to 100 °C, for 5 to 360 minutes, preferably 10 to 120 minutes.

[0060] The cured product formed by the method of the present invention is excellent in light transmittance. Specifically, the transmittance at 450 nm is 90% or more, and the haze value, which is a measure of the degree of turbidity, is 1 or less. The cured product of the present invention is suitable as a transparent member disposed between layers of a laminate such as an image display device or as a transparent member of an optical device.

[0061] (Laminate) The cured product of the present invention is suitable as a transparent member disposed between layers of a laminate such as an image display device. Such image display devices include a liquid crystal image display device, a liquid crystal image display element with a touch panel, an organic EL image display device, an organic EL image display element with a touch panel, a micro LED image display device, a micro LED image display device with a touch panel, a reflective image display device, and the like. All of these have a laminated structure in which various layers are stacked, and the cured product of the present invention is disposed between those layers and has a function of suppressing light reflection at the interface.

[0062] For example, since the cured product of the present invention has little coloring and is less likely to become turbid under high temperature or high temperature and high humidity, it is suitable as a material for forming an intermediate layer between the image display portion and the protective portion of an image display device. Examples of the base material of such an image display portion or protective portion include inorganic optical materials such as glass and ITO, or organic optical materials such as polycarbonate resin, acrylic resin, epoxy resin, and polystyrene resin. A transparent electrode may be formed on the surface of this optical member.

[0063] As a method for forming the cured product, for example, after applying the present composition to a film-like substrate, a tape-like substrate, or a sheet-like substrate, a hydrosilylation reaction is caused by irradiation with high-energy rays, leaving at room temperature, or heating at a low temperature to proceed with curing. Further, when the present composition is disposed between two substrates and cured to firmly bond both substrates, and when the present composition is smoothly applied to at least one surface of the substrate, semi-cured and made non-fluidized, and then both substrates are bonded together and further cured to firmly bond. The film thickness of this cured product is not limited, but is preferably 1 to 100,000 μm, more preferably 50 to 30,000 μm.

[0064] Since the present composition cures at a relatively low temperature, it can also be applied to the coating of a substrate with poor heat resistance. As such a substrate type, it is generally a transparent substrate such as glass, a synthetic resin film, sheet, or transparent electrode coating film. Further, examples of the coating method of the present composition include dispensing, gravure coating, microgravure coating, slit coating, slot die coating, screen printing, stencil printing, and comma coating.

[0065] (Method for forming a laminate) The first method of the method for forming the laminate of the present invention has the following steps. (iii) A step of applying a composition containing the components (A) to (D) onto a substrate and making the composition into a layer of the thickener or thermoplastic without irradiation with high-energy rays, (iv) A step of forming an upper layer member on the layer of the thickener or thermoplastic, and (v) A step of irradiating high-energy rays from above the upper layer member formed in the step (iV).

[0066] (Step iii) Step (iii) is the same step as step (i) of the method for producing the cured product, and the conditions are the same as above. However, in order to be able to perform the subsequent step of forming the upper layer member (bonding step) at a low temperature, it is preferable that the resulting product is a thickener.

[0067] (Step iv) Step (iv) is a step of laminating the layers arranged on the upper part, and there are various methods. However, in order to avoid entrapment of bubbles, it is preferable to perform lamination under vacuum or to add an operation of applying pressure in an autoclave after lamination to eliminate fine bubbles.

[0068] (Step v) Step (v) is a step of irradiating a high-energy ray from above the upper layer member formed in the above step (iV) to obtain a cured product. That is, it is a step of irradiating a high-energy ray through the transparent portion formed on the substrate and performing a curing reaction starting from the irradiation to obtain a cured product. The same step as step (ii) of the method for producing the cured product is performed with the upper and lower two layers sandwiched therebetween, and the conditions are the same as above. However, since the high-energy ray is irradiated through the layer, it is preferably at a higher irradiation dose.

[0069] The second method for forming the laminate of the present invention has the following steps. (vi) A step of applying the composition containing the components (A) to (D) on a substrate and turning the composition into a thickener or a thermoplastic without irradiation with a high-energy ray, (vii) A step of irradiating with a high-energy ray, (viii) A step of forming an upper layer member on the above thickener or thermoplastic, and (ix) A step of curing the above thickener or thermoplastic by heating or at room temperature.

[0070] (Step vi) Step (vi) is the same as step (iii) of the method for producing the cured product.

[0071] (Step vii) Step (vii) is the same as step (v) of the method for producing the cured product. However, in order to efficiently perform the subsequent lamination step, it is preferable to maintain the form as a thickener or a thermoplastic, particularly preferably as a thickener, without becoming a cured product within this step. Therefore, it is preferable to appropriately adjust the irradiation dose of the high-energy ray.

[0072] (Step viii) Step (viii) is the same as Step (iv) in the method for producing the cured product.

[0073] (Step ix) In Step (ix), since the high-energy ray-activated catalyst has already been activated in Step (vii), the reaction proceeds even at room temperature to obtain a cured product. However, in order to further accelerate the reaction, it is preferable to heat.

[0074] The third method for forming the laminate layer of the present invention has the following steps. (x) A step of applying a composition containing the components (A) to (D) onto a substrate and forming the composition into a thickened body or a thermoplastic layer without irradiating with high-energy rays, (xi) A step of irradiating the thickened body or thermoplastic layer obtained in the above Step (X) with high-energy rays, (xii) A step of forming an upper layer member on the thickened body or thermoplastic layer, and (xiii) A step of irradiating with high-energy rays from above the upper layer member formed by Step (Xii).

[0075] (Step x) Step (x) is the same as Step (vi) in the method for producing the cured product.

[0076] (Step xi) Step (xi) is the same as Step (vii) in the method for producing the cured product. However, in order to enhance the curing by high-energy ray irradiation in Step (xii), it is preferable to adjust the irradiation amount of high-energy rays.

[0077] (Step xii) Step (xii) is the same as Step (viii) in the method for producing the cured product.

[0078] (Step xiii) Step (xii) is a step of activating the inactive high-energy ray-activated catalyst in Step (x) to proceed with the hydrosilylation reaction to obtain a cured product.

[0079] (Optical device) Furthermore, the cured product of the present invention is suitable as a transparent member of an optical device. Such optical devices include light-receiving type display devices such as LCD (Liquid Crystal Display) and ECD (Electrochromic Display); light-emitting type display devices such as LED light-emitting devices and ELD (Electroluminescent Display), and various other lighting devices. The cured product of the present invention is used as an optical member such as a sealing agent for light-emitting elements or a lens material. By adhering or sticking between the display part such as liquid crystal or organic EL and the display forming members such as a touch panel and a cover lens, or between the display forming members with the cured product of the curable silicone composition of the present invention, the visibility of the optical display can be improved.

[0080] (Method for manufacturing an optical device) The method for forming the optical device of the present invention has the following steps. Step (ixv) Step (ixv) is a step of always forming a thermoplastic transparent film using the conditions for obtaining a thermoplastic in step (i) of the above, specifically, a step of smoothly applying the composition on the release film and partially advancing hydrosilylation to obtain a stable thermoplastic transparent film. There is no limitation on its film thickness, but practically it is in the range of 0.1 mm to 5 mm. Step (xv) Step (xv) is a step of cutting out the obtained thermoplastic transparent film to an appropriate size, peeling it from the release film, covering it on an optical device such as a light-emitting element, and heating to melt the thermoplastic transparent film to seal the light-emitting element. Step (xvi) Step (xvi) is a step of performing a hydrosilylation reaction starting from high-energy ray irradiation to obtain a cured product, similar to step (ii) above.

Example

[0081] A cured product was obtained from a composition containing the following components. In each average composition formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.

[0082] [Example 1] Average unit formula: (Me2ViSiO 1 / 2 ) 0.044 (Me3SiO 1 / 2 ) 0.411 (SiO 4 / 2 ) 0.545 3.5 parts by weight of vinyl-terminated branched-chain polysiloxane (A-1) represented by, average formula: ViMe2SiO(SiMe2O) 322 89.7 parts by weight of vinyl-terminated linear polysiloxane (A-2) represented by SiMe2Vi, 6.8 parts by weight of linear polysiloxane (B-1) represented by average formula: HMe2SiO(SiMe2O) 10 SiMe2H, a composition containing 5 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (C-1) as platinum atoms and 20 ppm of (methylcyclopentadienyl)trimethylplatinum(IV) (D-1) as platinum atoms was prepared. The viscosity of the composition was 1,800 mPa·s. After the composition was prepared and left standing for 10 minutes, the viscosity increased to 3,200 mPa·s. When the viscosity was measured immediately after irradiating the composition with ultraviolet rays at 365 nm from a 2W high-pressure mercury lamp at an irradiation dose of 5,000 mJ / cm 2 such that it became, it was found that the viscosity increased to 30,000 mPa·s or more, but the fluidity was maintained. However, it was confirmed that after ultraviolet irradiation, it gelled and became non-fluid after 5 minutes. When the hardness of the cured product was measured every 10 minutes by penetrometer, it was confirmed that the penetrometer stabilized at a constant value of 32 after 1 hour from ultraviolet irradiation, and the curing reaction was completed.

[0083] [Example 2] 3.5 parts by weight of the above A-1, 6.5 parts by weight of the above A-2, average composition formula: average formula: ViMe2SiO(SiMe2O) 53582.4 parts by weight of a vinyl-terminated linear polysiloxane (A-3) represented by SiMe2Vi, 4.6 parts by weight of the above B-1, 10 ppm as platinum atoms of the above C-1, and 20 ppm as the amount of platinum of the above D-1 were contained to prepare a composition. The viscosity of the composition was 8,200 mPa·s. After preparing the composition and leaving it standing for 10 minutes, the viscosity increased to 14,000 mPa·s. An ozone cut filter was irradiated with ultraviolet light at 365 nm from a 2W high-pressure mercury lamp so that the ultraviolet irradiation dose was 2500 mJ / cm 2 When the viscosity was measured immediately after irradiation, it had increased to 50,000 mPa·s or more, but the fluidity was maintained. However, it was confirmed that after ultraviolet irradiation, it gelled and became non-fluid after 10 minutes. When the hardness of the cured product was measured with a penetrometer every 10 minutes, it was confirmed that it stabilized at a constant penetrometer value of 35 after 1 hour from ultraviolet irradiation, indicating that the curing reaction was complete.

[0084] [Example 3] Average unit formula: (Me2ViSiO 1 / 2 ) 0.1 (Me3SiO 1 / 2 ) 0.4 (SiO 4 / 2 ) 0.5 55.7 parts by weight of a vinyl-terminated branched polysiloxane (A-4) represented by, average unit formula: (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 13.3 parts by weight of a branched polysiloxane (E-1) represented by, average formula: ViMe2SiO(SiMe2O) 160 1.7 parts by weight of a vinyl-terminated linear polysiloxane (A-3) represented by SiMe2Vi, average formula: HMe2SiO(SiMe2O) 400 24.6 parts by weight of a linear polysiloxane (B-2) represented by SiMe2H, average formula: Me3SiO(SiMe2O) 30 (SiMeHO) 30A linear polysiloxane (B-3) of SiMe3 in an amount of 4.7 parts by weight, the C-1 at 0.2 ppm as platinum atoms, and the D-1 at 5 ppm as platinum atoms were contained to prepare a composition. The viscosity of the composition was 3,500 mPa·s. The composition was heated at 90 °C for 30 minutes to obtain a thermoplastic that had no fluidity at 25 °C but had fluidity at 100 °C. The obtained thermoplastic did not lose its fluidity at 100 °C even after being stored at 25 °C for two months. This thermoplastic was irradiated with ultraviolet light at 365 nm with an irradiation dose of 2,500 mJ / cm 2 by a 2W high-pressure mercury lamp for an ozone cut filter, and then heated at 120 °C for 30 minutes to obtain a cured product with a Shore A hardness of 80.

[0085] [Example 4] A composition containing 32.2 parts by weight of the A-4, 28.5 parts by weight of the E-1, 20.7 parts by weight of the A-3, 15.7 parts by weight of the B-2, 2.9 parts by weight of the B-3, the C-1 at 0.1 ppm as platinum atoms and the D-1 at 5 ppm as platinum atoms was prepared. The viscosity of the composition was 2,800 mPa·s. The composition was heated at 90 °C for 30 minutes to obtain a thermoplastic that had no fluidity at 25 °C but had fluidity at 100 °C. The obtained thermoplastic did not lose its fluidity at 100 °C even after being stored at 25 °C for two months. This thermoplastic was irradiated with ultraviolet light at 365 nm with an irradiation dose of 2,500 mJ / cm 2 by a 2W high-pressure mercury lamp for an ozone cut filter, and then heated at 120 °C for 30 minutes to obtain a cured product with a Shore A hardness of 35.

[0086] [Example 5] The composition of Example 1 was applied onto a member in which a liquid crystal panel and a polarizing plate were integrated to a thickness of 200 μm using a bar coater. After application, within 5 minutes, ultraviolet light with an irradiation dose of 5,000 mJ / cm 2 at 365 nm was irradiated using a conveyor-type UV irradiation device. After irradiation, within 3 minutes, a cover glass was placed on it and left at room temperature. The cover glass initially moved when a force was applied from the lateral direction, but became difficult to move 5 minutes after UV irradiation and completely immovable 30 minutes after that.

[0087] [Example 6] Average composition formula: ViMe2SiO(SiMePhO) 36 Represented by SiMe2Vi 93.6% by weight of vinyl-terminated linear polysiloxane (A-5), average composition formula: (ViMe2SiO 1 / 2 )0.22(MeXSiO 2 / 2 )0.12(PhSiO 3 / 2 )0.66 (wherein X represents a glycidoxypropyl group), 1.0% by weight of vinyl group-containing polysiloxane (A-6), molecular formula: Ph2Si(OSiMe2H)2, linear polysiloxane (B-3) 3.9% by weight, average composition formula: (HMe2SiO 1 / 2 ) 0.6 (PhSiO 3 / 2 ) 0.4 A branched polysiloxane (B-4) represented by, 0.2% by weight of glycidoxypropyltrimethoxysilane, a composition containing 5 ppm of the above C-1 as platinum atoms and 20 ppm of the above D-1 as platinum atoms was prepared. The viscosity of the composition was 6,000 mPa·s. When the composition was left at 25°C for 10 minutes, a thickened product with a viscosity of about 12,000 mPa·s was obtained. This thermoplastic was irradiated with ultraviolet light at 365 nm with an ultraviolet irradiation dose of 2500 mJ / cm 2 through an ozone cut filter. After the ultraviolet light irradiation, the composition became non-fluid and changed to a gel 15 minutes later at 25°C, and a cured product with a penetration of 35 was obtained 40 minutes later at 25°C.

[0088] [Comparative Example 1] A composition containing 3.5 parts by weight of the above A-1, 89.7 parts by weight of the above A-2, 6.8 parts by weight of the above B-1, and 60 ppm of the above C-1 as platinum atoms was prepared. The viscosity of the composition was 1,800 mPa·s. Immediately after the composition was prepared, the composition generated heat and gelled after 1 minute, becoming non-fluid. The curing was too fast to prepare a test piece for penetration measurement, and the cured product was also colored brown.

[0089] [Comparative Example 2] A composition containing 3.5 parts by weight of the A-1, 89.7 parts by weight of the A-2, 6.8 parts by weight of the B-1, and 20 ppm of the D-1 as platinum atoms was prepared. The viscosity of the composition was 1,800 mPa·s. After the composition was prepared and left standing for 10 minutes, the viscosity of the composition with a constant viscosity of 1,800 mPa·s was measured immediately after irradiation with ultraviolet light at 365 nm from a 2W high-pressure mercury lamp at an irradiation dose of 5,000 mJ / cm 2 When measured, it had thickened to 3,200 mPa·s. After ultraviolet irradiation, it did not gel even after 1 hour. Therefore, when the composition was heated to 100 °C, it was confirmed that it gradually became non-fluid after 30 minutes.

[0090] [Comparative Example 3] A composition containing 55.7 parts by weight of the A-4, 13.3 parts by weight of the E-1, 1.7 parts by weight of the A-3, 24.6 parts by weight of the B-2, 4.7 parts by weight of the B-, and 2 ppm of the C-1 as platinum atoms was prepared. The viscosity of the composition was 3,500 mPa·s. The composition was heated at 90 °C for 30 minutes to obtain a cured product with a Shore A hardness of 80. Also, in order to obtain a softer cured product, when the above composition was heated at 50 °C for 30 minutes, a cured product with a Shore A hardness of 40 was obtained. However, the obtained cured product did not show high-temperature fluidity, and the cured product gradually increased in hardness over time and reached a Shore A hardness of 75 after 2 weeks at 25 °C.

[0091] [Comparative Example 4] A composition containing 32.2 parts by weight of the A-4, 28.5 parts by weight of the E-1, 20.7 parts by weight of the A-3, 15.7 parts by weight of the B-2, 2.9 parts by weight of the B-3, 0.1 ppm of the C-1 as platinum atoms, and 5 ppm of the D-1 as platinum atoms was prepared. The viscosity of the composition was 2,800 mPa·s. The composition was heated at 90 °C for 30 minutes, but no change was observed in the composition.

[0092] [Comparative Example 5] A composition containing 94.0 parts by weight of the A-2, 4.1 parts by weight of the B-2, 1.4 parts by weight of the B-3, and 5 ppm of the C-1 as platinum atoms was prepared. The viscosity of the composition was 2,100 mPa·s. The composition gelled after 30 minutes at 25°C.

[0093] [Comparative Example 6] The composition of Comparative Example 2 was applied using a bar coater onto a member in which a liquid crystal panel and a polarizing plate were integrated so that the thickness became 200 μm. After application, within 5 minutes, ultraviolet rays with an irradiation dose of 5000 mJ / cm at 365 nm were irradiated using a conveyor-type UV irradiation device. 2 After irradiation, within 3 minutes, a cover glass was placed on it and left at room temperature. Liquid gradually leaked out from the edge of the cover glass, and it did not cure even 30 minutes after ultraviolet irradiation.

[0094] [Comparative Example 7] A composition containing 93.6 wt% of the A-5, 1.0 wt% of the A-6, 3.9 wt% of the B-3, 1.3 wt% of the B-4, 0.2 wt% of glycidoxypropyltrimethoxysilane, and 5 ppm of the C-1 as platinum atoms was prepared. The viscosity of the composition was 6,000 mPa·s. When the composition was left at 25°C for 10 minutes, a thickened product with a viscosity of about 12,000 mPa·s was obtained. This thermoplastic was irradiated with ultraviolet rays at 365 nm with an irradiation dose of 2500 mJ / cm through an ozone cut filter using a 2W high-pressure mercury lamp. 2 After ultraviolet irradiation, after 60 minutes at 25°C, the composition gradually became non-fluid and changed into a gel, but it was found that the penetration continued to decrease even after 2 hours at 25°C and the curing reaction was not complete. [Industrial Applicability]

[0095] The method for producing the organopolysiloxane cured product of the present invention can be rapidly cured at low temperature while having a sufficient pot life at room temperature, so it is suitable as a method for forming a laminate between layers of an image display device.

Claims

1. A method for producing an organopolysiloxane cured product, comprising: Step (i): The following components (A) to (D) (A) A mixture of the following components (a1) and (a2): (a1) General formula: R63SiO(R62SiO)m1SiR63 (In the formula, each R6 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group. In one molecule, at least two R6 at the molecular chain ends are alkenyl groups having 2 to 12 carbon atoms, and at least 30 mol% of all R6 are aryl groups. m1 is an integer in the range of 5 to 1,000.) A linear organopolysiloxane having an alkenyl group having 2 to 12 carbon atoms at the molecular chain ends, represented by (a2) Average unit formula: (R ５ ３ SiO １／２ ) ｍ (R ５ ２ SiO ２／２ ) ｎ (R ５ SiO ３／２ ) ｏ (SiO ４／２ ) ｐ (In the formula, R ５ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and m, n, o and p are the following conditions: m + n + o + p = 1, 0.2 ≤ m ≤ 0.5, 0 ≤ n ≤ 0.3, 0 ≤ o ≤ 0.8, 0 ≤ p ≤ 0.6, 0.2 ≤ o + p ≤ 0.

8. The organopolysiloxane resin represented by these conditions.) (B) The following average composition formula (2): H ｃ R ３ ｄ SiO （４－ｃ－ｄ）／２ (2) (In the formula, R ３ is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group, and c and d are the following conditions: 1 ≦ c + d ≦ 3 and 0.01 ≦ c / (c + d) ≦ 0.33), the amount of silicon atom-bonded hydrogen atoms in this component is in the range of 0.5 to 2 moles with respect to 1 mole of the total alkenyl groups in the organopolysiloxane (A) component represented by the formula, (C) A first hydrosilylation reaction catalyst that exhibits activity in this composition without irradiation with high-energy rays, and (D) A second hydrosilylation reaction catalyst that does not exhibit activity without irradiation with high-energy rays but exhibits activity in this composition upon irradiation with high-energy rays, carrying out a hydrosilylation reaction on the composition containing them without irradiation with high-energy rays to obtain a thickener having fluidity at room temperature or a thermoplastic that is non-fluid at room temperature but exhibits fluidity at 100°C, and Step (ii): irradiating the thickener or thermoplastic obtained in the above step (i) with high-energy rays. A method comprising.

2. The method for producing an organopolysiloxane cured product according to claim 1, wherein the high-energy ray is any one selected from ultraviolet rays, gamma rays, X-rays, alpha rays, or electron beams.

3. The method for producing an organopolysiloxane cured product according to claim 1, wherein the component (B) is an organohydrogenpolysiloxane represented by the following average unit formula (3): (HR 4 2 SiO 1 / 2 ) e (R 4 3 SiO 1 / 2 ) f (HR 4 SiO 2 / 2 ) g (R 4 2 SiO 2 / 2 ) h (HSiO 3 / 2 ) i (R 4 SiO 3 / 2 ) j (SiO 4 / 2 ) k (R 5 O 1 / 2 ) l (3) (In the formula, R ４ is each independently a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group, and R ５ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and e, f, g, h, i, j, k, and l are the following conditions: e + f + g + h + i + j + k = 1, 0 ≦ l ≦ 0.1, 0.01 ≦ e + g + i ≦ 0.2, 0 ≦ e ≦ 0.6, 0 ≦ g ≦ 0.6, 0 ≦ i ≦ 0.4, 0.01 ≦ e + f ≦ 0.8, 0.01 ≦ g + h ≦ 0.8, 0 ≦ i + j ≦ 0.6.)

4. The method for producing an organopolysiloxane cured product according to any one of claims 1 to 3, wherein the molar ratio ((C) / (D)) of the component (C) to the component (D) is 0.001 to 1000.

5. A method for producing a laminate in which an organopolysiloxane cured product is disposed between layers, comprising: Step (iii): The following components (A) to (D) (A) A mixture of the following components (a1) and (a2): (a1) General formula: R63SiO(R62SiO)m1SiR63 ​ (In the formula, each R6 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group. In one molecule, at least two R6 at the molecular chain terminals are alkenyl groups having 2 to 12 carbon atoms, and at least 30 mol% of all R6 are aryl groups. m1 is an integer in the range of 5 to 1,000.) A linear organopolysiloxane having an alkenyl group having 2 to 12 carbon atoms at the molecular chain terminals, (a2) Average unit formula: (R ５ ３ SiO １／２ ) ｍ (R ５ ２ SiO ２／２ ) ｎ (R ５ SiO ３／２ ) ｏ (SiO ４／２ ) ｐ (wherein, R ５ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and m, n, o and p are the following conditions: m + n + o + p = 1, 0.2 ≦ m ≦ 0.5, 0 ≦ n ≦ 0.3, 0 ≦ o ≦ 0.8, 0 ≦ p ≦ 0.6, 0.2 ≦ o + p ≦ 0.8), an organopolysiloxane resin represented by (B) The following average composition formula (2): H ｃ R ３ ｄ SiO （４－ｃ－ｄ）／２ (2) (In the formula, R ３ is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group, and c and d are the following conditions: 1 ≤ c + d ≤ 3 and 0.01 ≤ c / (c + d) ≤ 0.

33. The amount such that the silicon atom-bonded hydrogen atoms in this component are in the range of 0.5 to 2 moles with respect to 1 mole of the total alkenyl groups in the organopolysiloxane (A) component represented by)) (C) A first hydrosilylation reaction catalyst that exhibits activity in this composition without irradiation with high-energy rays, and (D) A second hydrosilylation reaction catalyst that does not exhibit activity without irradiation with high-energy rays but exhibits activity in this composition upon irradiation with high-energy rays, A step of applying a composition containing the above onto a substrate and performing a hydrosilylation reaction without irradiation with high-energy rays to form a thickener having fluidity at room temperature or a thermoplastic layer that is non-fluid at room temperature but exhibits fluidity at 100 °C, Step (iV): A step of forming an upper layer member on the thickener or thermoplastic layer obtained in the above step (iii), and Step (V): A step of irradiating the thickener or thermoplastic layer with high-energy rays from at least one of under the substrate, on the upper layer member, or the side surface of the thickener or thermoplastic layer, A method containing the above.

6. A method for producing a laminate in which an organopolysiloxane cured product is disposed between layers, Step (Vi): The following components (A) to (D) (A) A mixture of the following (a1) component and (a2) component: (a1) General formula: R63SiO(R62SiO)m1SiR63 (In the formula, each R6 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group. In one molecule, at least two R6 at the molecular chain terminals are alkenyl groups having 2 to 12 carbon atoms, and at least 30 mol% of all R6 are aryl groups. m1 is an integer in the range of 5 to 1,000.) A linear organopolysiloxane having an alkenyl group having 2 to 12 carbon atoms at the molecular chain terminals, (a2) Average unit formula: (R ５ ３ SiO １／２ ) ｍ (R ５ ２ SiO ２／２ ) ｎ (R ５ SiO ３／２ ) ｏ (SiO ４／２ ) ｐ (wherein R ５ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and m, n, o and p are the following conditions: m + n + o + p = 1, 0.2 ≦ m ≦ 0.5, 0 ≦ n ≦ 0.3, 0 ≦ o ≦ 0.8, 0 ≦ p ≦ 0.6, 0.2 ≦ o + p ≦ 0.8), an organopolysiloxane resin represented by (B) The following average composition formula (2): H ｃ R ３ ｄ SiO （４－ｃ－ｄ）／２ (2) (In the formula, R ３ is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group, and c and d are the following conditions: 1 ≤ c + d ≤ 3 and 0.01 ≤ c / (c + d) ≤ 0.

33. The amount of the silicon atom-bonded hydrogen atom in this component is in the range of 0.5 to 2 moles with respect to 1 mole of the total alkenyl groups in the organopolysiloxane (A) component represented by the formula) (C) A first hydrosilylation reaction catalyst that exhibits activity in this composition without irradiation with high-energy rays, and (D) A second hydrosilylation reaction catalyst that does not exhibit activity without irradiation with high-energy rays but exhibits activity in this composition upon irradiation with high-energy rays, A step of applying a composition containing the same onto a substrate, performing a hydrosilylation reaction without irradiation with high-energy rays, and forming a thickening body having fluidity at room temperature or a thermoplastic layer that is non-fluid at room temperature but shows fluidity at 100 °C, Step (Vii): A step of irradiating the thickening body or the thermoplastic layer obtained in the above step (Vi) with high-energy rays, Step (Viii): A step of forming an upper layer member on the thickening body or the thermoplastic layer irradiated with the high-energy rays, and Step (iX): A step of curing the thickening body or the thermoplastic layer by heating or leaving it at room temperature, A method comprising the above.

7. A method for producing a laminate in which an organopolysiloxane cured product is disposed between layers, Step (X): The following components (A) to (D) (A) A mixture of the following (a1) component and (a2) component: (a1) General formula: R63SiO(R62SiO)m1SiR63 (In the formula, each R6 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group. In one molecule, at least two R6 at the molecular chain ends are alkenyl groups having 2 to 12 carbon atoms, and at least 30 mol% of all R6 are aryl groups. m1 is an integer in the range of 5 to 1,000.) A linear organopolysiloxane having an alkenyl group having 2 to 12 carbon atoms at the molecular chain ends, represented by (a2) Average unit formula: (R ５ ３ SiO １／２ ) ｍ (R ５ ２ SiO ２／２ ) ｎ (R ５ SiO ３／２ ) ｏ (SiO ４／２ ) ｐ (In the formula, R ５ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and m, n, o and p are the following conditions: m + n + o + p = 1, 0.2 ≦ m ≦ 0.5, 0 ≦ n ≦ 0.3, 0 ≦ o ≦ 0.8, 0 ≦ p ≦ 0.6, 0.2 ≦ o + p ≦ 0.

8. The numbers that satisfy the conditions) an organopolysiloxane resin represented by, (B) The following average composition formula (2): H ｃ R ３ ｄ SiO （４－ｃ－ｄ）／２ (2) (In the formula, R ３ is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group, and c and d are the following conditions: 1 ≤ c + d ≤ 3 and 0.01 ≤ c / (c + d) ≤ 0.

33. The amount of the silicon atom-bonded hydrogen atom in this component is in the range of 0.5 to 2 moles with respect to 1 mole of the total of the alkenyl groups in the organopolysiloxane (A) component represented by)) (C) A first hydrosilylation reaction catalyst that shows activity in this composition without irradiation with high-energy rays, and (D) A second hydrosilylation reaction catalyst that does not show activity without irradiation with high-energy rays but shows activity in this composition by irradiation with high-energy rays, A step of applying a composition containing the same onto a substrate, performing a hydrosilylation reaction without irradiation with high-energy rays, and forming a thickening body having fluidity at room temperature or a thermoplastic layer that is non-fluid at room temperature but shows fluidity at 100 °C, Step (Xi): A step of irradiating the thickening body or the thermoplastic layer obtained in the above step (X) with high-energy rays, Step (Xii): A step of forming an upper layer member on the thickening body or the thermoplastic layer irradiated with the high-energy rays, and Step (Xiii): A step of irradiating the thickening body or the thermoplastic layer with high-energy rays from at least one of under the substrate, on the upper layer member, or the side surface of the thickening body or the thermoplastic layer, A method comprising the above.

8. A method for forming an optical device having an organopolysiloxane cured product formed on its surface, Process (ixv): The following components (A) to (D) (A) A mixture of the following components (a1) and (a2): (a1) General formula: R63SiO(R62SiO)m1SiR63 (In the formula, each R6 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group. In one molecule, at least two R6 at the molecular chain ends are alkenyl groups having 2 to 12 carbon atoms, and at least 30 mol% of all R6 are aryl groups. m1 is an integer in the range of 5 to 1,000.) A linear organopolysiloxane having an alkenyl group having 2 to 12 carbon atoms at the molecular chain ends, represented by (a2) Average unit formula: (R ５ ３ SiO １／２ ) ｍ (R ５ ２ SiO ２／２ ) ｎ (R ５ SiO ３／２ ) ｏ (SiO ４／２ ) ｐ (In the formula, R ５ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and m, n, o, and p are the following conditions: m + n + o + p = 1, 0.2 ≦ m ≦ 0.5, 0 ≦ n ≦ 0.3, 0 ≦ o ≦ 0.8, 0 ≦ p ≦ 0.6, 0.2 ≦ o + p ≦ 0.

8. The numbers that satisfy the conditions), an organopolysiloxane resin represented by (B) The following average composition formula (2): H ｃ R ３ ｄ SiO （４－ｃ－ｄ）／２ (2) (In the formula, R ３ is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group, and c and d are the following conditions: 1 ≤ c + d ≤ 3 and 0.01 ≤ c / (c + d) ≤ 0.33), the amount of silicon atom-bonded hydrogen atoms in this component is in the range of 0.5 to 2 moles with respect to a total of 1 mole of alkenyl groups in the organopolysiloxane (A) component represented by), (C) A first hydrosilylation reaction catalyst that shows activity in this composition without irradiation with high-energy rays, and (D) A second hydrosilylation reaction catalyst that does not show activity without irradiation with high-energy rays but shows activity in this composition by irradiation with high-energy rays, A step of applying the composition containing these on a release film and performing a hydrosilylation reaction without irradiation with high-energy rays to form a thermoplastic film that is non-fluid at room temperature but shows fluidity at 100°C, Process (xv): A step of installing the above thermoplastic film on an optical device and heating it, Process (xvi): A step of irradiating the thermoplastic film obtained in the above process (xv) or its melt with high-energy rays, A method having these.