Polymerizable composition, glass laminate, and method for producing the same

Abstract

The present invention provides a polymer composition that exhibits high adhesion to a glass substrate and a glass laminate using the same. [Solution] The polymerizable composition of the present invention comprises a polythiol compound (A), an isocyanate compound (B), and an alkoxysilane compound (D) having one or more functional groups selected from the group consisting of a mercapto group, an isocyanate group, a ureido group, and an isocyanurate group.

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition, a glass laminate, and a method for producing the same. More specifically, it relates to a polymerizable composition, a polymerized and cured product thereof, a glass laminate, and a method for producing the same. [Background technology]

[0002] To date, various industrial products have used materials such as plastics, metals, paper, wood, textiles, leather, glass, rubber, ceramics, and concrete. While these materials are sometimes used individually, in many cases, composite materials are formed by combining two or more materials to achieve higher functionality and lower costs. Forming such composite materials requires technology to join dissimilar materials.

[0003] For example, Patent Document 1 discloses a laminate in which a film made of plastic polyester or thermoplastic polycarbonate, an intermediate layer containing a predetermined urethane resin, and an inorganic glass lens substrate are sequentially laminated, with respect to improving the adhesion between the film and the inorganic glass lens substrate.

[0004] Furthermore, as an adhesive, Patent Document 2 discloses an adhesive comprising a two-component curable gas barrier composition containing agent A, which contains a polythiol adduct of an aromatic ring-containing polyisocyanate, and agent B, which contains a polyol and / or a polythiol. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2017-211548 [Patent Document 2] Japanese Patent Publication No. 2023-95101 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the technology described in Patent Document 1 uses an intermediate layer between a glass substrate and a film made of plastic polyester or thermoplastic polycarbonate, and did not consider a resin film that is directly bonded to the glass substrate. Furthermore, the adhesive containing a thiourethane group described in Patent Document 2 had room for improvement in terms of adhesion to the glass substrate.

[0007] This invention provides a polymer composition that exhibits high adhesion to a glass substrate and a glass laminate using the same. [Means for solving the problem]

[0008] The inventors of the present invention conducted diligent research to solve the above problems and discovered that by combining a composition containing a polythiol compound (A) and an isocyanate compound (B) with an alkoxysilane compound (D) having a predetermined functional group, it is possible to improve adhesion to a glass substrate while maintaining good curability, thus completing the present invention.

[0009] According to the present invention, the following polymer compositions and technologies relating to glass laminates using the same are provided.

[0010] [1] A polymerizable composition comprising a polythiol compound (A), an isocyanate compound (B), and an alkoxysilane compound (D) having one or more functional groups selected from the group consisting of a mercapto group, an isocyanate group, a ureido group, and an isocyanurate group. [2] The polymerizable composition according to [1], wherein the alkoxysilyl group of the alkoxysilane compound (D) is selected from the group consisting of a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, and an ethyldiethoxysilyl group. [3] The polymerizable composition according to [1] or [2], wherein the total content of the polythiol compound (A) and the isocyanate compound (B) is 100% by mass, and the content of the alkoxysilane compound (D) is 1 to 20% by mass. [4] A polymerizable composition according to any one of [1] to [3], wherein the polythiol compound (A) comprises a polythiol compound with three or more functions. [5] The polythiol compound (A) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)- A polymerizable composition according to any one of [1] to [4], comprising one or more selected from the group consisting of 1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane. [6] The polymerizable composition according to any one of [1] to [5], wherein the isocyanate compound (B) contains one or more selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. [7] The polymerizable composition according to any one of [1] to [6], further comprising a boron-based photopolymerization initiator (C). [8] The polymerizable composition according to [7], wherein the boron-based photopolymerization initiator (C) contains a base generator composed of an organic boron anion and a counter cation. [9] The polymerizable composition according to [7] or [8], wherein the boron-based photopolymerization initiator (C) contains one or two selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). [Chemical formula] (In formula (1), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, and R5 to R8 each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group and phenanthryl group may be substituted by a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group.) [Chemical formula] (In formula (2), R1 to R7 each independently represent an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and R8 to R Each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group, and the phenyl group, the naphthyl group, the anthracenyl group and the phenanthryl group may be substituted by a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group.)

[10] The polymerizable composition according to any one of [1] to [9], further comprising a tin catalyst (E).

[11] The film stress measured by the following procedure is 1.8 to 5.0 (kg / mm 2 ) The polymerizable composition according to any one of [1] to

[10] . (Procedure) (1) Drop 1 g of the polymerizable composition at the long side end of a cover glass substrate having a length of 50 mm, a width of 22 mm, and a thickness of 0.19 mm, and use a film applicator (set to a gap of 150 μm and a scanning speed of 1 m / min) to apply it uniformly. (2) Cover the surface of the cover glass substrate coated with the polymerizable composition with a release film (thickness 100 μm, polyethylene terephthalate). (3) While moving an LED-UV irradiator (irradiation intensity UVA 1074 mW / cm 2 , UVC 97.8 mW / cm 2 ) from one end of the cover glass to the other end at a scanning speed of 1 m / min, irradiate the polymerizable composition coated on the cover glass substrate through the release film with UV light. Then, stop the irradiation, return the LED-UV irradiator to its original position, and then, while moving from one end of the cover glass to the other end at a scanning speed of 1 m / min again, irradiate the polymerizable composition coated on the cover glass substrate through the release film with UV light for the second time. (4) Heat the cover glass substrate covered with the release film at 130 °C for 60 minutes to complete the polymerization. Then, peel off the release film to obtain a cover glass substrate with a polymerized cured product layer of the polymerizable composition, which is used as a measurement sample. (5) The measurement sample is placed on a flat table with the polymerized cured material layer side facing down and the cover glass substrate side facing up, and the height (mm) at which the distance between the polymerized cured material layer side of the measurement sample and the flat table is maximized is measured. (6) When the initial length of the cover glass substrate (50 mm) is taken as the arc length of the measurement sample, the radius of curvature R (mm) formed by the measurement sample is calculated using the arc length and the arrow height (mm) by the Newton-Raphson method. (7) The obtained radius of curvature R (mm) and the Young's modulus E (kg / mm) of the cover glass substrate. 2 ), Poisson's ratio Vs, thickness t (mm), and the thickness T (mm) of the polymerized hardened layer are determined, and the film stress (kg / mm) is calculated by applying these values ​​to the following formula. 2 Calculate ).

number

[12] A polymerizable composition according to any one of [1] to

[11] , used in optical waveguides.

[13] A polymerized cured product of any one of the polymerizable compositions described in [1] to

[12] .

[14] A polymerized film comprising a polymerized cured product of any one of the polymerizable compositions described in [1] to

[12] . A glass laminate comprising a polymerized cured product described in

[15]

[13] and a glass substrate.

[16] The glass laminate according to

[15] , wherein the thickness of the polymerized cured product is 50 to 500 μm.

[17] The glass laminate according to

[15] or

[16] , wherein the haze of the polymerized cured product is 0.1 to 1%.

[18] The glass laminate according to any one of

[15] to

[17] , wherein the thickness of the glass substrate is 300 to 3000 μm.

[19] The glass laminate according to any one of

[15] to

[18] , wherein the refractive index of the glass substrate is 1.6 to 2.4.

[20] The glass laminate according to any one of

[15] to

[19] , wherein the glass substrate comprises titanium oxide or niobium oxide.

[21] A step of preparing a polymerizable composition according to any one of [1] to

[12] , The following steps (i) and (ii); Step (i) After coating the polymerizable composition onto a substrate, a glass substrate is pressed onto the coated polymerizable composition to polymerize and cure the polymerizable composition. Step (ii) A step of coating the polymerizable composition onto a glass substrate, pressing a substrate against the polymerizable composition, and polymerizing and curing the polymerizable composition. At least one of the following steps, A method for manufacturing a glass laminate having the following characteristics.

[22] The substrate has a pattern on the order of nanometers, A method for producing a glass laminate according to

[21] , wherein the obtained polymerized cured product has a nanoimprint structure.

[23] The step of preparing the polymerizable composition is: A step of mixing the polythiol compound (A), a portion of the isocyanate compound (B), and an alkoxysilane compound (D) to obtain a prepolymer, A step of preparing a polymerization solution containing the remainder of the isocyanate compound (B), Includes, A method for producing a glass laminate according to

[21] or

[22] , comprising mixing the prepolymer and the polymerization solution to obtain a polymerizable composition. [Effects of the Invention]

[0011] According to the present invention, a polymer composition that exhibits high adhesion to a glass substrate and a glass laminate using the same can be provided. [Modes for carrying out the invention]

[0012] Embodiments of the present invention are described below. In these embodiments, unless otherwise specified, "A~B" indicating a numerical range represents A or greater and B or less. Furthermore, when numerical ranges are described in steps, the upper and lower limits of each numerical range can be arbitrarily combined.

[0013] In this embodiment, "film" is a concept that includes what is generally referred to as a "sheet". In this embodiment, thiourethane refers to a compound having a thiourethane bond formed by the reaction of a polythiol component and an isocyanate component.

[0014] <Polymerizable composition> The polymerizable composition of this embodiment comprises a polythiol compound (A), an isocyanate compound (B), and an alkoxysilane compound (D) having one or more functional groups selected from the group consisting of a mercapto group, an isocyanate group, a ureido group, and an isocyanurate group.

[0015] According to our research, we have found that by including an alkoxysilane compound (D) having one or more functional groups selected from the group consisting of mercapto groups, isocyanate groups, ureido groups, and isocyanurate groups, high adhesion to a glass substrate can be obtained while maintaining good curability.

[0016] Although the details of the reason are not clear, it is presumed that the functional groups of the alkoxysilane compound (D), such as the mercapto group, isocyanate group, ureido group, and isocyanurate group, all exhibit good compatibility with the polythiol compound (A) and the isocyanate compound (B). This suppresses thickening and rapid reactions, and while maintaining good curability, the alkoxysilane group acts on the glass surface to improve adhesion.

[0017] Furthermore, since the alkoxysilane compound (D) has high transparency and refractive index, it can maintain the high transparency and refractive index of the glass substrate in the glass laminate described later. In addition, since the polymerizable composition of this embodiment has reduced shrinkage during curing, even if the polymerizable composition of this embodiment is cured and laminated on a thin glass substrate, deformation or damage to the thin glass substrate due to curing shrinkage of the polymerizable composition can be suppressed. On the other hand, if the adhesion is low, when the polymerizable composition is cured and laminated on a thin glass substrate, delamination from the glass substrate will occur due to curing shrinkage. In other words, there is a trade-off relationship between adhesion and suppression of deformation of the glass substrate, and the polymerizable composition of this embodiment can achieve a higher level of both adhesion and suppression of deformation of the glass substrate.

[0018] The following describes each component contained in the polymerizable composition.

[0019] [Polythiol compound (A)] The photopolymerizable composition in the thiourethane film of this embodiment contains a bifunctional or more polythiol (A). This allows for the formation of a thiourethane bond between a bifunctional or more polythiol (A) and an isocyanate compound (B), which will be described later. Polythiols are highly nucleophilic and highly reactive with isocyanate compounds.

[0020] Examples of polythiol compounds with two or more functions (A) include polythiol compounds with two or more functions, and polythiol compounds with three or more functions.

[0021] (Bifunctional polythiols) Examples of bifunctional polythiols include methanedithiol, ethanedithiol, 1,3-propanedithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl) ether, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) disulfide, bis (Mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and esters of these with thioglycolic acid and mercaptopropionic acid; Bis(2-mercaptoethyl) sulfide, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl Aliphatic polythiol compounds such as tyl disulfide bis(3-mercaptopropinate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiglycolate bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), dithiodiglycolate bis(2-mercaptoethyl ester), dithiodipropionate bis(2-mercaptoethyl ester), and 4,6-bis(mercaptomethylthio)-1,3-dithiane; Aromatic polythiol compounds such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol; Examples include heterocyclic polythiol compounds such as 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenediol, bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane.

[0022] Among these, it is more preferable that the bifunctional polythiol includes one or more selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0023] (Polythiols with three or more functionalities) Examples of polythiols with three or more functions include 1,2,3-propanetrithiol, tetrakis(mercaptomethyl)methane, trimethylolpropanetris(2-mercaptoacetate), trimethylolpropanetris(3-mercaptopropionate), trimethylolethanetris(2-mercaptoacetate), trimethylolethanetris(3-mercaptopropionate), pentaerythritoltetrakis(2-mercaptoacetate), pentaerythritoltetrakis(3-mercaptopropionate), 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, and 1,2,3-tris(3-mercaptomethylthio)propane. Topropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, their thioglycolate esters and mercaptopropionate esters; Aliphatic polythiol compounds such as 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane; Aromatic polythiol compounds such as 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, and 1,3,5-tris(mercaptoethyleneoxy)benzene; Examples include heterocyclic polythiol compounds such as 2,4,6-trimercapto-s-triazine, 2,4,6-trimercapto-1,3,5-triazine, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane.

[0024] Examples of polythiols with three or more functions include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, and 2-(2,2-bis(mercapto It is preferable to include one or more selected from the group consisting of tomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane; more preferably to include one or more selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and pentaerythritoltetrakis(3-mercaptopropionate); and even more preferably to include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0025] In particular, the polythiol compound (A) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis( It is preferable to include one or more selected from the group consisting of mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane. Including a polythiol compound with three or more functions makes it easier to achieve hardness.

[0026] Furthermore, the polythiol compound (A) of this embodiment may include a polythiol compound with three or more functions, or it may include both a bifunctional polythiol compound and a polythiol compound with three or more functions. For example, the polythiol compound with three or more functions may include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or it may include one or more bifunctional polythiols selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is a polythiol with three or more functions.

[0027] [Isocyanate compound (B)] The isocyanate compound (B) is preferably pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, It comprises one or more selected from the group consisting of tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate, and more preferably one or more selected from the group consisting of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and xylylene diisocyanate.

[0028] Furthermore, the isocyanate compound (B) preferably comprises an aromatic isocyanate compound (B) from the viewpoint of further improving polymerization curability, and more preferably comprises one or more selected from the group consisting of xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.

[0029] The equivalent ratio of the isocyanate group in the isocyanate compound (B) to the active hydrogen-containing group in the polythiol compound (A) (active hydrogen-containing group / isocyanato group) is preferably 0.8 or higher, more preferably 0.85 or higher, even more preferably 0.9 or higher, and preferably 1.2 or lower, more preferably 1.15 or lower, and even more preferably 1.1 or lower. This allows for proper curing while suppressing curing shrinkage.

[0030] The total content of the polythiol compound (A) and the isocyanate compound (B) in the polymerizable composition of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, even more preferably 98% by mass or more, and preferably less than 100% by mass, when the total polymerizable composition is considered as 100% by mass.

[0031] [Boron-based photopolymerization initiator (C)] The polymerizable composition of this embodiment may further contain a boron-based photopolymerization initiator (C). Boron-based photopolymerization initiator (C) is an initiator capable of photopolymerization and contains boron. This further promotes the polymerization of polymerizable compositions and yields good polymerized cured products.

[0032] Furthermore, the boron-based photopolymerization initiator (C) of this embodiment is an initiator capable of photopolymerization, and preferably contains a base generator from the viewpoint of further improving photopolymerizability. The base-generating agent preferably includes a compound consisting of an organoboron anion and a countercation. The organoboron anion preferably comprises one or more selected from the group consisting of a phenyl group, an alkyl group, and an aryl group, and more preferably comprises one or more selected from the group consisting of a phenyl group and an alkyl group. The countercation preferably comprises one or more selected from the group consisting of ammonium or ammonium salts, and more preferably comprises an ammonium salt.

[0033] The base-generating agent more preferably includes one or more compounds selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2).

[0034] [ka]

[0035] In formula (1), R1 to R4 preferably each independently represent an alkyl group having 1 to 8 carbon atoms, and R5 to R8 preferably each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthrill group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0036] In formula (1), R1 to R4 are preferably the same. R1 to R4 are more preferably alkyl groups having 2 to 5 carbon atoms, even more preferably linear alkyl groups, and even more preferably n-butyl groups. In formula (1), R8 is more preferably an alkyl group having 2 to 5 carbon atoms, even more preferably a linear alkyl group, and even more preferably an n-butyl group. In formula (1), R5 to R7 are preferably the same. R5 to R7 are more preferably a phenyl group, a butylphenyl group, or a naphthyl group, and even more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. If R5 to R7 contain an aromatic ring, the aromatic ring may be substituted with an alkyl group, an aryl group, or the like.

[0037] The compound represented by formula (1) preferably contains one or more selected from the group consisting of tetra(n-butyl)ammonium=n-butyltriphenyl borate, tetra(n-butyl)ammonium=n-butyltri(4-tert-butylphenyl) borate, tetra(n-butyl)ammonium=n-butyltri(1-naphthyl) borate, and tetra(n-butyl)ammonium=n-butyltri(4-methyl-1-naphthyl) borate. The "=" in the compound name signifies an ionic bond. Among these, from the viewpoint of further improving the performance balance of solubility, polymerizability, and pot life, the compound represented by the formula (1) more preferably contains one or two selected from the group consisting of tetra(n-butyl)ammonium = n-butyltriphenylborate and tetra(n-butyl)ammonium = n-butyltri(1-naphthyl)borate.

[0038] [Chemical formula]

[0039] In formula (2), R1 to R7 each independently represent an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and R8 to R 11 each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted by a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0040] In formula (2), R1 to R7 are preferably the same. R1 to R7 are preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. In formula (2), R 11 is more preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. In formula (2), R8 to R 10 are preferably the same. R8 to R 10 are more preferably a phenyl group, a butylphenyl group, or a naphthyl group, and even more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. R8 to R 10 When containing an aromatic ring, the aromatic ring may be substituted by an alkyl group, an aryl group, or the like.

[0041] The aforementioned compounds consisting of organoboron anions and countercations can also be commercially available. Examples of commercially available products include WPBG-300 and WPBG-345 (both manufactured by Fujifilm Corporation).

[0042] When the total content of the polythiol compound (A) and the isocyanate compound (B) is 100% by mass, the content of the boron-based photopolymerization initiator (C) is preferably 0.05 to 2% by mass, and more preferably 0.1 to 1% by mass. By setting the content of the boron-based photopolymerization initiator (C) to above the lower limit mentioned above, photocuring can be performed efficiently, and polymerization can be completed. On the other hand, by keeping the content of the boron-based photopolymerization initiator (C) below the above upper limit, yellowing of the resin can be suppressed.

[0043] [Alkoxysilane compound (D)] The alkoxysilane compound (D) of this embodiment has one or more functional groups selected from the group consisting of mercapto groups, isocyanate groups, ureido groups, and isocyanurate groups. That is, by specifying the functional groups, thickening and rapid reactions can be suppressed, thereby improving adhesion to the glass substrate while obtaining good polymerization curability. Furthermore,

[0044] Furthermore, the alkoxysilyl group possessed by the alkoxysilane compound (D) is selected from the group consisting of a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, and an ethyldiethoxysilyl group.

[0045] Examples of the above-mentioned alkoxysilane compounds (D) having a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane. Examples of commercially available products include KBM-802, KBM-803, X-12-1154, and X-12-1156 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the above-mentioned alkoxysilane compound (D) having an isocyanate group include 3-isocyanate-propyltriethoxysilane. Commercially available examples include KBE-9007 and X-12-1159L manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the alkoxysilane compound (D) having the ureido group mentioned above include 3-ureidopropyltrialkoxysilane. A commercially available example is KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the alkoxysilane compound (D) having the isocyanurate group mentioned above include tris-(trimethoxysilylpropyl)isocyanurate. A commercially available example is KBM-9659 manufactured by Shin-Etsu Chemical Co., Ltd.

[0046] When the total content of the polythiol compound (A) and the isocyanate compound (B) is 100% by mass, the content of the alkoxysilane compound (D) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 11% by mass. By increasing the content of alkoxysilane compound (D) to above the lower limit mentioned above, adhesion to the glass substrate can be improved. On the other hand, by keeping the content of alkoxysilane compound (D) below the above upper limit, it is possible to suppress the decrease in refractive index while maintaining adhesion to glass.

[0047] [Tin catalyst (E)] The polymerizable composition of this embodiment may further contain a tin catalyst (E). By forming a prepolymer with the tin catalyst (E), a certain isocyanate compound (B), and a polythiol compound (A), the viscosity can be increased, improving the coatability.

[0048] Examples of the tin catalyst (E) include tin acetate, tin octoate, tin oleate, tin laurate, monobutyltin trioctate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dimethyltin dichloride, and dibutyltin dichloride. Preferably, one or two selected from the group consisting of dimethyltin dichloride and dibutyltin dichloride are used.

[0049] From the viewpoint of further improving polymerizability, the content of the tin catalyst (E) is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and even more preferably 0.001 parts by mass or more, per 100 parts by mass of the total of the polythiol compound (A) and the isocyanate compound (B), while preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, and even more preferably 0.003 parts by mass or less.

[0050] [Other ingredients] The polymerizable composition of this embodiment may further contain ultraviolet absorbers, antioxidants, light stabilizers, sensitizers, mold release agents, solvents, bluing agents, IR cutters, blue light cutters, reactive diluents, oil-soluble dyes, pigments, colorants, fragrances, fillers, adhesion enhancers such as coupling agents, chain extenders, crosslinking agents, defoamers, anti-settling agents, dispersants, plasticizers, anti-sagging agents, antifouling agents, preservatives, bactericides, antimicrobial agents, antifungal agents, matting agents, thickeners, pigment dispersants, anti-repellent agents, scratch-resistant enhancers, slip agents, surface modifiers, color separation preventatives, emulsifiers, anti-skinning agents, drying agents, antistatic agents, conductive agents (electrostatic additives), flame retardants, thermal conductivity improvers, plasticizers, ion exchange resins, etc.

[0051] Examples of release agents include acidic phosphate ester compounds, polyether-modified silicones, alkyl-modified silicones, polyester-modified silicones, dimethylpolysiloxane, polyoxyalkylene glycol monoalkyl ether compounds, polyoxyalkylene glycol monoester compounds, fluorine atom-containing compounds, surfactants, nonionic surfactants, acrylic surfactants, and the like.

[0052] The amount of release agent in the polymerizable composition of this embodiment is preferably 100 ppm or more, more preferably 500 ppm or more, even more preferably 1000 ppm or more, even more preferably 1500 ppm or more, and preferably 5000 ppm or less, more preferably 4500 ppm or less, even more preferably 4000 ppm or less, and even more preferably 3500 ppm or less, relative to the total amount of the polythiol compound (A) and the isocyanate compound (B).

[0053] Next, the properties of the polymerizable composition of this embodiment will be described.

[0054] [Membrane stress] The polymerizable composition of this embodiment has a film stress of 1.8 to 5.0 kg / mm² as measured by the following procedure. 2 Preferably, it is 1.8 to 4.0 (kg / mm 2 It is more preferable that the value be 1.8 to 3.5 (kg / mm 2 It is even more preferable that the ratio is 1.8 to 3.0 (kg / mm²). 2 It is especially preferable that the film stress is below the above upper limit. By keeping the film stress below the upper limit, it is possible to reduce the resin stress during curing shrinkage of the polymerizable composition while obtaining high adhesion to the glass substrate. As a result, when the polymerizable composition of this embodiment is applied to a glass substrate, deformation of the glass substrate can be suppressed.

[0055] (procedure) (1) Drop 1 g of the polymerizable composition onto the long edge of a cover glass substrate measuring 50 mm in length, 22 mm in width, and 0.19 mm in thickness, and apply it uniformly using a film applicator (set to a gap of 150 μm and a scanning speed of 1 m / min). (2) A release film (100 μm thick, made of polyethylene terephthalate resin) is placed over the surface of the cover glass substrate to which the polymerizable composition has been applied. (3)LED-UV irradiator (irradiation intensity UVA1074mW / cm 2 UVC 97.8 mW / cm² 2 The LED-UV irradiator is moved from one end of the cover glass to the other at a scanning speed of 1 m / min, and UV light is irradiated onto the polymerizable composition coated on the cover glass substrate via the release film. After that, the irradiation is stopped, the LED-UV irradiator is returned to its original position, and then, again, the LED-UV irradiator is moved from one end of the cover glass to the other at a scanning speed of 1 m / min, and UV light is irradiated onto the polymerizable composition coated on the cover glass substrate via the release film for a second time. (4) The cover glass substrate covered with the release film is heated at 130°C for 60 minutes to complete the polymerization. After that, the release film is peeled off to obtain a cover glass substrate with a polymerized cured product layer of the polymerizable composition, which is used as a measurement sample. (5) The measurement sample is placed on a flat table with the polymerized cured material layer side facing down and the cover glass substrate side facing up, and the height (mm) at which the distance between the polymerized cured material layer side of the measurement sample and the flat table is maximized is measured. (6) When the initial length of the cover glass substrate (50 mm) is taken as the arc length of the measurement sample, the radius of curvature R (mm) formed by the measurement sample is calculated using the arc length and the arrow height (mm) by the Newton-Raphson method. (7) The obtained radius of curvature R (mm) and the Young's modulus E (kg / mm) of the cover glass substrate. 2 ), Poisson's ratio Vs, thickness t (mm), and the thickness T (mm) of the polymerized hardened layer are determined, and the film stress (kg / mm) is calculated by applying these values ​​to the following formula. 2 Calculate ).

[0056]

number

[0057] The polymerizable composition exhibiting the above-mentioned film stress can be achieved by adjusting the selection and combination of a polythiol compound (A), an isocyanate compound (B), a boron-based photopolymerization initiator (C), and an alkoxysilane compound (D) having one or more functional groups selected from the group consisting of mercapto groups, isocyanate groups, ureido groups, and isocyanurate groups, or by devising a method for producing the polymerizable composition as described later. Specifically, examples include selecting a manufacturing method according to the raw materials, including a step in the manufacturing method of the polymerizable composition in which a polythiol compound (A), the isocyanate compound (B), and an alkoxysilane compound (D) are mixed to obtain a prepolymer, and selecting curing conditions according to the manufacturing method.

[0058] [Application] The polymerizable composition of this embodiment can be suitably used, for example, as a core material for optical waveguides. Furthermore, since the polymerizable composition of this embodiment has good embedding properties, it can form fine patterns on the order of nanometers. For example, by pressing the polymerizable composition of this embodiment onto a mold with a nanometer-order fine pattern, polymerizing and curing it, and then removing the mold, a polymerized and cured product with a nanometer-order fine pattern can be obtained.

[0059] <Method for producing polymerizable compositions> Next, an example of a method for producing the polymerizable composition described above will be explained. The method for producing the polymerizable composition of this embodiment includes the following steps in order. (1) A step of mixing a polythiol compound (A), the isocyanate compound (B), and an alkoxysilane compound (D) to obtain a prepolymer. (2) Step of preparing a polymerization solution containing the isocyanate compound (B) (3) A step of mixing the prepolymer and the polymerization solution.

[0060] [Process (1)] Step (1) is a step of mixing a polythiol compound (A), a portion of the isocyanate compound (B), and an alkoxysilane compound (D) to obtain a prepolymer. To enable viscosity adjustment of the prepolymer and facilitate control of coating properties, it is preferable to first mix the polythiol compound (A) with an optional component such as a tin catalyst (E) and a mold release agent, then further add and mix the alkoxysilane compound (D), and then further add and mix a portion of the isocyanate compound (B).

[0061] The heating temperature during mixing is preferably 70°C or higher, more preferably 75°C or higher, from the viewpoint of moderately increasing the viscosity of the prepolymer, and preferably 90°C or lower, more preferably 85°C or lower, from the viewpoint of preventing the viscosity of the prepolymer from increasing too much. The mixing method can be a known method.

[0062] [Process (2)] Step (2) is a step of preparing a polymerization solution containing the remainder of the isocyanate compound (B). The remainder of the isocyanate compound (B) is the total amount of isocyanate compound (B) minus the amount of isocyanate compound (B) added in step (1). Preferably, the polymerization solution in step (2) further contains a boron-based photopolymerization initiator (C). The mixing method is not particularly limited and can be any known method.

[0063] [Process (3)] Step (3) is a step of mixing the prepolymer and the polymerization solution. The mixing method is not particularly limited and can be any known method. The manufacturing method of this embodiment includes a step of preparing the prepolymer and polymerization solution separately and then mixing them. This makes it possible to adjust the viscosity using only mixture A, which contains only a metal catalyst as a catalyst. By mixing the prepolymer and polymerization solution immediately before applying the polymerizable composition, it becomes easier to adjust the viscosity of the entire polymerizable composition to an appropriate range when applied. Furthermore, by adjusting the heating temperature and time to maintain an appropriate viscosity range, the viscosity increase of the prepolymer can be suppressed even during long-term storage, and the viscosity required for thick, uniform application can be maintained when mixed with the polymerization solution and applied. Furthermore, by adjusting the viscosity of the prepolymer to an appropriate range, the increase in viscosity during storage can be suppressed, making it possible to manufacture, transport, and store only the prepolymer.

[0064] The method for producing the polymerizable composition of this embodiment is not limited to the method described above, and other methods may be used. For example, a polythiol compound (A), an isocyanate compound (B), an arbitrary boron-based photopolymerization initiator (C), and an alkoxysilane compound (D) may be mixed together.

[0065] <Polymerized cured product> The polymerized cured product of this embodiment may be obtained by irradiating the polymerizable composition with ultraviolet light to polymerize a portion of the polymerizable composition, and then heating the polymerizable composition to further polymerize and cure it, or it may be obtained by polymerizing and curing by heating without ultraviolet light irradiation.

[0066] Ultraviolet light includes UVC with wavelengths of 250-260 nm and UVA with wavelengths of 320-390 nm, and it is UVC that affects photopolymerization. When using ultraviolet light, light sources such as sunlight, chemical lamps, mercury lamps, metal halide lamps, and UV LEDs can be used.

[0067] The heating temperature when heating the polymerizable composition is preferably 80°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher, while preferably 140°C or lower, and more preferably 130°C or lower, from the viewpoint of allowing the polymerizable composition to polymerize more sufficiently. The heating time when heating the polymerizable composition is preferably 10 minutes or more, more preferably 30 minutes or more, even more preferably 50 minutes or more, even more preferably 60 minutes or more, and preferably 300 minutes or less, more preferably 150 minutes or less, even more preferably 120 minutes or less, even more preferably 100 minutes or less, and even more preferably 80 minutes or less.

[0068] <Polymerized film> The polymerized film of this embodiment is a film made of the polymerizable composition described above. The polymerized film of this embodiment can be obtained, for example, by applying the polymerizable composition described above onto a release film, placing another release film on top of it, irradiating the polymerizable composition with release films on both sides with ultraviolet light to polymerize a portion of the polymerizable composition, then heating the polymerizable composition to further polymerize and cure it, and finally peeling off the release film.

[0069] <Glass laminate> The glass laminate of this embodiment is formed by laminating a polymerized cured product and a glass substrate. In particular, from the viewpoint of obtaining good adhesion, it is preferable that the polymerized cured product is laminated directly onto the surface of the glass substrate. Furthermore, the polymerized cured product is preferably in the form of layers, and may cover one side of the glass substrate or cover the entire surface of one side of the glass substrate.

[0070] Furthermore, the glass laminate may be formed by laminating the polymerized cured material so as to be in direct contact with one surface of the glass substrate, or by laminating the polymerized cured material so as to be in direct contact with both surfaces of the glass substrate. Furthermore, since the polymerizable composition of this embodiment exhibits reduced curing shrinkage, deformation of the glass substrate can be suppressed even when the polymerized cured material is laminated on one side of the glass substrate. Additionally, by laminating the polymerized cured material so that it is in direct contact with both sides of the glass substrate, resin stress can be dispersed, effectively suppressing deformation of the glass substrate.

[0071] The polymerized cured product of this embodiment may be obtained by applying the above polymerizable composition onto a substrate using conventionally known methods such as a bar coater, spin coater, or dip coater, but it is preferable to apply it directly onto glass.

[0072] The thickness of the polymerized cured product is preferably 50 to 500 μm, and more preferably 100 to 300 μm. By making the thickness of the polymerized cured product equal to or greater than the lower limit mentioned above, it becomes easier to improve its adhesion to the glass substrate. On the other hand, by keeping the thickness of the polymerized cured product below the above upper limit, it becomes easier to suppress damage to the glass substrate due to curing shrinkage.

[0073] From the viewpoint of further improving transparency, the haze of the polymerized cured product is preferably 3% or less, more preferably 1% or less, and even more preferably 0.8% or less. On the other hand, there is no lower limit to the haze, but it may be, for example, 0.1% or more, or 0.2% or more.

[0074] Haze can be measured in accordance with JIS K7136:2000.

[0075] The thickness of the glass substrate is preferably 200 to 2000 μm, more preferably 300 to 1500 μm, and even more preferably 400 to 1000 μm. By setting the thickness of the glass substrate to be above the lower limit mentioned above, it becomes easier to suppress damage to the glass substrate due to curing shrinkage. On the other hand, by keeping the thickness of the glass substrate below the above upper limit, it is possible to reduce the weight of the glass laminate.

[0076] The refractive index of the glass substrate is preferably 1.6 to 2.4, more preferably 1.65 to 2.0, and even more preferably 1.7 to 1.9. The refractive index is measured at a temperature of 23°C.

[0077] The glass substrate preferably contains titanium oxide or niobium oxide. This provides good transparency, processability, and adhesion.

[0078] The glass laminate may also include other layers, such as protective layers and functional layers, depending on its application, and the number of layers is not particularly limited. For example, it may include a silane coating layer. Furthermore, the glass laminate may be subjected to known surface treatments, such as corona treatment, ozone treatment, and plasma treatment.

[0079] [Application] Glass laminates can be used as display components, display components for AR (Augmented Reality) and VR (Virtual Reality) devices, and as components, they can be used as optical waveguides.

[0080] <Method for manufacturing glass laminates> Next, an example of a method for manufacturing the above-mentioned glass laminate will be described. The method for manufacturing the glass laminate of this embodiment is: A step of preparing a polymerizable composition, The following steps (i) and (ii); Step (i) a step of coating the polymerizable composition onto a substrate, pressing a glass substrate onto the coated polymerizable composition to polymerize and cure the polymerizable composition, and Step (ii) A step of coating a glass substrate with the polymerizable composition, pressing the substrate against the polymerizable composition, and polymerizing and curing the polymerizable composition. At least one of the following steps, It has.

[0081] Specifically, step (i) laminates a polymerizable film onto the lower surface of the glass substrate, and step (ii) laminates a polymerized cured product onto the upper surface of the glass substrate. If the glass laminate has a polymerized cured product on only one side of the glass substrate, either step (i) or step (ii) may be included. If the glass laminate has a polymerized cured product on both sides of the glass substrate, steps (i) and (ii) may be performed in any order or simultaneously.

[0082] Polymerization curing can be carried out under the same conditions as described above for the polymerized cured product. Alternatively, the polymerizable composition may be irradiated with ultraviolet light to polymerize a portion of it and cure it, and then the polymerizable composition may be heated to further polymerize and cure it. This suppresses the reaction of unreacted isocyanate groups in the isocyanate compound (B), which would increase the hygroscopicity of the cured polymerizable composition, and thus suppresses appearance defects caused by the generation of bubbles or water bubbles at the interface of the glass laminate.

[0083] Furthermore, while there are no restrictions on the formation of a film using a polymerizable composition, it can be done, for example, by arranging two glass plates with a predetermined gap between them, placing a PTFE sheet around all four sides of the glass plates, injecting the polymerizable composition, and then securing the two glass plates together with clips.

[0084] Furthermore, the polymerizable composition can be applied by conventionally known methods such as bar coaters, spin coaters, dip coaters, and roll-to-roll coaters.

[0085] Furthermore, a release film can be used on the substrate. That is, a release film may be interposed between the substrate and the coated polymerizable composition. The release film includes at least one selected from the group consisting of polyethylene terephthalate and fluororesin.

[0086] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention. [Examples]

[0087] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0088] 1. Preparation of polymerizable composition Polymerizable compositions for the examples and comparative examples shown in Table 1 were prepared using the following raw materials. In Table 1, "-" indicates the absence of a component. (raw materials) <Polythiol compound (A)> A1; A mixture mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (manufactured by Mitsui Chemicals, Inc.) A2; A mixture mainly composed of 4,7-bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol (manufactured by Mitsui Chemicals, Inc.) <Isocyanate compound (B)> • B1; Xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (manufactured by Mitsui Chemicals, Inc.) <Boron-based photopolymerization initiator (C)> • C1; Tetrabutylammonium butyltriphenyl borate (manufactured by Resonaq, "P3B") <Alkoxysilane compound (D)> • D1; Mercapto group-containing alkoxysilane (Shin-Etsu Chemical Co., Ltd., 3-mercaptopropyltrimethoxysilane "KBM-803") • D2; Mercapto group-containing polyfunctional alkoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "X-12-1154") • D3; Isocyanate group-containing alkoxysilane (Shin-Etsu Chemical Co., Ltd., 3-isocyanatetopropyltriethoxysilane "KBE-9007") • D4; Isocyanate group-containing polyfunctional alkoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "X-12-1159L") <Tin catalyst (E)> • E1; Dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd., "Nestin P") <Release agent> • KF-351A; Polyether-modified silicone (manufactured by Shin-Etsu Silicone Co., Ltd. as "KF-351A")

[0089] [When preparing a prepolymer and then undergoing UV irradiation and thermal polymerization] <Example 1> (Polymerizable composition) 45.45 parts by weight of polythiol compound (A1) was mixed with 0.30 parts by weight of a release agent and 0.001 parts by weight of tin catalyst (E1), and the mixture was stirred and dissolved. Then, 3.18 parts by weight of alkoxysilane compound (D1) was added and the mixture was stirred for 15 minutes. Subsequently, 13.71 parts by weight of isocyanate compound (B1) was added and the mixture was stirred for 15 minutes. The mixture was then degassed with a vacuum pump and heated in an 80°C bath for 4.5 hours while stirring. After heating, the temperature was lowered to 20°C to prepare prepolymer solution B. Polymer solution A was prepared by adding 0.30 parts by weight of a boron-based photopolymerization initiator (C1) to 37.06 parts by weight of an isocyanate compound (B1) and stirring for 15 minutes. Polymer solution A was added to prepolymer solution B and stirred and mixed. After mixing, the mixture was degassed under vacuum to obtain a polymerizable composition. (Glass laminate) A 10cm square glass plate (1mm thick) was prepared, and the polymerizable composition obtained was coated onto one surface of the glass plate to a thickness of 200μm using a variable applicator (BEVS 1806B / 150). After coating, a release film was placed on the surface coated with the polymerizable composition. Subsequently, LED-UV (wavelength 365nm) was irradiated. The integrated UVA light intensity was 6230mJ / cm². 2 The irradiation intensity was 1075 mW / cm². 2 The material was then heated at 130°C for 60 minutes to complete polymerization, and a laminate was obtained by stacking the glass plate, polymerized cured product, and release film in that order. After that, the release film was peeled off to obtain a glass laminate.

[0090] <Example 2> A polymerizable composition and a glass laminate were obtained using the same procedure as in Example 1, except that the amount of polythiol compound (A1) in prepolymer liquid B of Example 1 was 43.99 parts by weight, the amount of alkoxysilane compound (D1) was 5.24 parts by weight, the amount of isocyanate compound (B1) was 13.55 parts by weight, and the amount of isocyanate compound (B1) in polymerization liquid A was 36.62 parts by weight.

[0091] <Example 3> A polymerizable composition and a glass laminate were obtained using the same procedure as in Example 1, except that the amount of polythiol compound (A1) in prepolymer solution B of Example 1 was 41.86 parts by weight, the amount of alkoxysilane compound (D1) was 8.23 ​​parts by weight, the amount of isocyanate compound (B1) in polymerization solution A was 13.31 parts by weight, and the amount of isocyanate compound (B1) in polymerization solution A was 35.99 parts by weight.

[0092] <Comparative Example 1> A polymerizable composition and a glass laminate were obtained using the same procedure as in Example 1, except that the amount of polythiol compound (A1) in prepolymer solution B of Example 1 was 47.71 parts by weight, the alkoxysilane compound (D1) was omitted, the isocyanate compound (B1) was 13.96 parts by weight, and the isocyanate compound (B1) in polymerization solution A was 37.73 parts by weight.

[0093] <Example 11> A polymerizable composition and a glass laminate were obtained using the same procedure as in Example 1, except that 45.45 parts by weight of polythiol compound (A1) in prepolymer liquid B of Example 1 was replaced with 44.29 parts by weight of polythiol compound (A2), 5.21 parts by weight of alkoxysilane compound (D1), 9.98 parts by weight of isocyanate compound (B1), and 39.92 parts by weight of isocyanate compound (B1) in polymerization liquid A.

[0094] <Comparative Example 2> A polymerizable composition and a glass laminate were obtained using the same procedure as in Example 1, except that 45.45 parts by weight of polythiol compound (A1) in prepolymer liquid B of Example 1 was replaced with 48.01 parts by weight of polythiol compound (A2), alkoxysilane compound (D1) was not used, isocyanate compound (B1) was 10.28 parts by weight, and isocyanate compound (B1) in polymerization liquid A was 41.11 parts by weight.

[0095] [When preparing the product without prepolymerization and then undergoing UV irradiation and thermal polymerization] <Example 4> 43.99 parts by weight of polythiol compound (A1) was mixed with 0.30 parts by weight of a release agent and stirred until dissolved. Then, 5.24 parts of polymerization of alkoxysilane compound (D1) were added and stirred for 15 minutes to obtain a mixture. Separately, 50.17 parts by weight of isocyanate compound (B1) was mixed with 0.30 parts by weight of boron-based photopolymerization initiator (C1) and stirred for 15 minutes. This mixture was then added to the above mixture, stirred for another 15 minutes, and then degassed under vacuum to obtain a polymerizable composition. A glass laminate was obtained using the obtained polymerizable composition in the same procedure as in Example 1.

[0096] <Example 5> A polymerizable composition was obtained using the same procedure as in Example 4, except that the amount of polythiol compound (A1) was 43.48 parts by weight, the amount of alkoxysilane compound (D1) was 5.24 parts by weight, the amount of alkoxysilane compound (D2) was 6.32 parts by weight, and the amount of isocyanate compound (B1) was 49.59 parts by weight. A glass laminate was obtained using the obtained polymerizable composition using the same procedure as in Example 1.

[0097] <Example 10> A polymerizable composition was obtained using the same procedure as in Example 4, except that 43.99 parts by weight of polythiol compound (A1) in Example 4 was replaced with 44.29 parts by weight of polythiol compound (A2), 5.21 parts by weight of alkoxysilane compound (D1), and 49.90 parts by weight of isocyanate compound (B1). A glass laminate was obtained using the obtained polymerizable composition using the same procedure as in Example 1.

[0098] <Example 6> 45.77 parts by weight of polythiol compound (A1) was mixed with 0.30 parts by weight of a release agent, and the mixture was stirred and dissolved to obtain a mixed solution. Separately, 47.11 parts by weight of isocyanate compound (B1) was mixed with 0.30 parts by weight of boron-based photopolymerization initiator (C1), and the mixture was stirred. Then, 6.52 parts by weight of alkoxysilane compound (D3) was added and the mixture was stirred for 15 minutes. This mixture was then gradually added to the above mixture, stirred for 15 minutes, and then degassed under vacuum to obtain a polymerizable composition. A glass laminate was obtained using the obtained polymerizable composition in the same procedure as in Example 1.

[0099] <Example 7> A polymerizable composition was obtained using the same procedure as in Example 6, except that the amount of polythiol compound (A1) was 44.44 parts by weight, the amount of isocyanate compound (B1) was 45.75 parts by weight, and the amount of alkoxysilane compound (D3) was 6.52 parts by weight, and the amount of alkoxysilane compound (D4) was 9.21 parts by weight. A glass laminate was obtained using the obtained polymerizable composition using the same procedure as in Example 1.

[0100] [When preparing the product without prepolymerization and performing thermal polymerization only] <Example 8> (Polymerizable composition) 50.17 parts by weight of isocyanate compound (B1) was mixed with 0.01 parts by weight of tin catalyst (E1) and 0.30 parts by weight of mold release agent, and the mixture was stirred for 15 minutes. Then, 43.99 parts by weight of polythiol compound (A1) was added and the mixture was stirred for another 15 minutes to obtain a mixed solution. Alkoxysilane compound (D1) was added to the above mixture in a 5.24 polymerization portion and stirred for 15 minutes, then degassed under vacuum to obtain a polymerizable composition. (Glass laminate) A 10cm square glass plate (1mm thick) was prepared, and the polymerizable composition obtained was coated onto one surface of the glass plate to a thickness of 200μm using a variable applicator (BEVS 1806B / 150). After coating, a release film was placed on the surface coated with the polymerizable composition. The resulting laminate was placed in an electric furnace, and polymerization was completed by raising the temperature according to the program. The temperature program started at 30°C and increased the temperature in each step: from 30°C to 50°C in 2 hours, from 50°C to 80°C in 6 hours, from 80°C to 100°C in 2 hours, and from 100°C to 120°C in 1 hour.

[0101] <Example 9> A polymerizable composition was obtained using the same procedure as in Example 8, except that the isocyanate compound (B1) was 49.90 parts by weight, the polythiol compound (A1) was 43.99 parts by weight, the polythiol compound (A2) was 44.29 parts by weight, and the alkoxysilane compound (D1) was 5.21 parts by weight. A glass laminate was obtained using the obtained polymerizable composition using the same procedure as in Example 8.

[0102] <Example 12> (Polymerized film) 45.45 parts by weight of polythiol compound (A1) was mixed with 0.30 parts by weight of a release agent and 0.001 parts by weight of tin catalyst (E1), and the mixture was stirred and dissolved. Then, 3.18 parts by weight of alkoxysilane compound (D1) was added and the mixture was stirred for 15 minutes. Subsequently, 13.71 parts by weight of isocyanate compound (B1) was added and the mixture was stirred for 15 minutes. The mixture was then degassed with a vacuum pump and heated in an 80°C bath for 4.5 hours while stirring. After heating, the temperature was lowered to 20°C to prepare prepolymer solution B. Polymer solution A was prepared by adding 0.30 parts by weight of a boron-based photopolymerization initiator (C1) to 37.06 parts by weight of an isocyanate compound (B1) and stirring for 15 minutes. Polymer solution A was added to prepolymer solution B and stirred and mixed. After mixing, the mixture was degassed under vacuum to obtain a polymerizable composition. The obtained polymerizable composition was adjusted to a viscosity of 300 mPa·s and coated onto a release film (100 μm thick, "Unipeel TR-1," manufactured by Unitika Corporation) using a variable applicator (BEVS 1806B / 150) to a thickness of 200 μm. Then, another release film was placed on both sides of the polymerizable composition using a laminator (Royal Sovereign RSC-382). Subsequently, LED-UV (wavelength 365 nm) was irradiated. The integrated UVA light intensity was 6230 mJ / cm². 2The irradiation intensity was 1075 mW / cm². 2 The film was then heated at 130°C for 60 minutes to complete polymerization, and the release films placed on both sides were peeled off to obtain the polymerized film. The resulting polymerized film had a thickness of 200 μm, a haze of 0.57, and a YI of 0.98.

[0103] 2. Measurement The following measurements were performed on the prepared polymerizable composition and glass laminate. The results are shown in Table 1.

[0104] [Membrane stress] The film stress was measured using the following procedure. Note that "*" in Table 1 indicates that the cured layer had delaminated from the glass substrate, making measurement impossible. (procedure) A cover glass substrate (Premium Cover Glass, manufactured by Fisher Scientific) measuring 50 mm in length, 22 mm in width, and 0.19 mm in thickness was washed with a solvent. 1 g of the polymerizable composition was then dropped onto the long edge of the substrate and applied uniformly using a film applicator (set to a gap of 150 μm and a scanning speed of 1 m / min). A release film (100 μm thick, "Unipeel TR-1," manufactured by Unitika Corporation) was placed over the surface coated with the polymerizable composition, ensuring no air bubbles were trapped. An LED-UV irradiator (SUNG HO LED, MS-B3701AF-N2) was used, with an irradiation intensity of UVA 1074 mW / cm². 2 UVC 97.8 mW / cm² 2The polymerizable composition coated on the cover glass substrate via the release film was irradiated with UV light while moving the LED-UV irradiator from one end to the other of the cover glass at a scanning speed of 1 m / min. After that, the irradiation was stopped and the LED-UV irradiator was returned to its original position, and then the polymerizable composition coated on the cover glass substrate via the release film was irradiated with UV light a second time while moving the LED-UV irradiator from one end to the other of the cover glass at a scanning speed of 1 m / min. The cover glass substrate covered with the release film was heated at 130°C for 60 minutes to complete the polymerization. After that, the release film was peeled off to obtain a cover glass substrate having a cured layer of the polymerizable composition, which was used as a measurement sample. The obtained measurement sample was placed on a flat table with the cured material layer side facing down and the cover glass substrate side facing up, and the arrow height (mm) at which the distance between the cured material layer side of the measurement sample and the flat table was maximized was measured. The radius of curvature R (mm) was calculated using the Newton-Raphson method, with the initial length of the cover glass substrate (50 mm) as the arc length of the measurement sample, and the arrow height (mm). Membrane stress (kg / mm 2 ) is the radius of curvature R (mm) and the Young's modulus E (kg / mm) of the cover glass substrate. 2 The Poisson's ratio Vs, thickness t (mm), and thickness T (mm) of the cured layer were determined and then applied to the following formula to calculate the result. Note that Young's modulus E is the same as that of borosilicate glass, which has a Young's modulus of 7290 kg / mm². 2 The Poisson's ratio Vs was set to 0.21. The thickness of the substrate was measured using a thickness gauge.

[0105]

number

[0106] [Viscosity of prepolymer; vibrating viscometer, 25°C] The viscosity (mPa·s) at 23°C was measured using a Sekonic VM-10A-M vibrating viscometer.

[0107] [Thickness of the polymerized cured layer and glass substrate] The thickness was measured at 10 arbitrary locations using a Digimatic indicator (ID-H0560, manufactured by Mitutoyo Corporation), and the average value of these measurements was used for each measurement.

[0108] [Haze in the polymerized hardened layer] Haze was measured in accordance with JIS K7136.

[0109] [YI value of the polymerized hardened layer] The YI values ​​were measured in accordance with ASTM E313-96 using a Konica Minolta CM-5 spectrophotometer under a C light source of 2°, and the average value (3 measurements) was adopted for each measurement.

[0110] [Refractive index of polymerized hardened layer (nd)] The refractive index was measured using an Abbe refractometer (manufactured by Atago) at a measurement temperature of 23°C.

[0111] 3. Evaluation The following evaluations were conducted. The results are shown in Table 1.

[0112] [Adhesion to glass] A cross-cut test was conducted in accordance with JIS K5600. Specifically, the surface of the polymerized hardened layer of the glass laminate was cut in a grid pattern using a cutter, cellophane tape (manufactured by Nichiban) was applied, and the percentage of the peeled area after peeling was calculated and evaluated according to the following criteria. ·standard A: Less than 10% of the area has peeled off. B: Peeled area is 10% or more, but less than 50% C: Peeled area is 50% or more, but less than 100% D: 100% of the area has been peeled off.

[0113] [Peeling] The interface condition of the glass laminate was visually inspected and evaluated according to the following criteria. ·standard A (None): There was no peeling at all. B (present): Delamination was observed.

[0114] [Deformation (visual inspection)] When a glass laminate was placed on a plane with the glass surface facing downwards, the height at which the edge of the glass laminate lifted off the plane was measured and evaluated according to the following criteria. ·standard A (None): Height is less than 3% of the length of the glass substrate. B (Yes): Height is 3% or more of the length of the glass substrate.

[0115] [Table 1]

Claims

1. A polymerizable composition comprising a polythiol compound (A), an isocyanate compound (B), and an alkoxysilane compound (D) having one or more functional groups selected from the group consisting of a mercapto group, an isocyanate group, a ureido group, and an isocyanurate group.

2. The polymerizable composition according to claim 1, wherein the alkoxysilyl group of the alkoxysilane compound (D) is selected from the group consisting of a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, and an ethyldiethoxysilyl group.

3. The polymerizable composition according to claim 1 or 2, wherein when the total content of the polythiol compound (A) and the isocyanate compound (B) is 100% by mass, the content of the alkoxysilane compound (D) is 1 to 20% by mass.

4. The polymerizable composition according to claim 1 or 2, wherein the polythiol compound (A) comprises a polythiol compound with three or more functions.

5. The polythiol compound (A) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl A polymerizable composition according to claim 1 or 2, comprising one or more selected from the group consisting of tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, and tris(mercaptomethylthio).

6. The polymerizable composition according to claim 1 or 2, wherein the isocyanate compound (B) comprises one or more selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

7. The polymerizable composition according to claim 1 or 2, further comprising a boron-based photopolymerization initiator (C).

8. The polymerizable composition according to claim 7, wherein the boron-based photopolymerization initiator (C) comprises a base generator consisting of an organoboron anion and a countercation.

9. The polymerizable composition according to claim 7, wherein the boron-based photopolymerization initiator (C) comprises one or two compounds selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). 【Chemistry 1】 (In formula (1), R １ ~R ４ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, R ５ ~R ８ Each of these independently represents a C1-C8 alkyl group, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthrill group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group. 【Chemistry 2】 (In formula (2), R １ ~R ７ Each of these independently represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, R ８ ~R １１ Each of these independently represents a C1-C8 alkyl group, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthrill group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

10. The polymerizable composition according to claim 1 or 2, further comprising a tin catalyst (E).

11. The film stress measured by the following procedure is 1.8 to 5.0 (kg / mm ２ ), the polymerizable composition according to claim 1 or 2. (procedure) (1) Drop 1 g of the polymerizable composition onto the long edge of a cover glass substrate measuring 50 mm in length, 22 mm in width, and 0.19 mm in thickness, and apply it uniformly using a film applicator (set to a gap of 150 μm and a scanning speed of 1 m / min). (2) A release film (100 μm thick, polyethylene terephthalate) is placed over the surface of the cover glass substrate on which the polymerizable composition is applied. (3) LED-UV irradiator (irradiation intensity UVA1074mW / cm ２ , UVC97.8mW / cm ２ The LED-UV irradiator is moved from one end of the cover glass to the other end at a scanning speed of 1 m / min, and UV light is irradiated onto the polymerizable composition coated on the cover glass substrate via the release film. After that, the irradiation is stopped, and the LED-UV irradiator is returned to its original position, and then, again, the LED-UV irradiator is moved from one end of the cover glass to the other end at a scanning speed of 1 m / min, and UV light is irradiated onto the polymerizable composition coated on the cover glass substrate via the release film for a second time. (4) The cover glass substrate covered with the release film is heated at 130°C for 60 minutes to complete the polymerization. After that, the release film is peeled off to obtain a cover glass substrate with a polymerized cured product layer of the polymerizable composition, which is used as a measurement sample. (5) The measurement sample is placed on a flat table with the polymerized cured material layer side facing down and the cover glass substrate side facing up, and the height (mm) at which the distance between the polymerized cured material layer side of the measurement sample and the flat table is maximized is measured. (6) When the initial length of the cover glass substrate (50 mm) is taken as the arc length of the measurement sample, the radius of curvature R (mm) formed by the measurement sample is calculated using the arc length and the arrow height (mm) by the Newton-Raphson method. (7) The obtained radius of curvature R (mm) and the Young's modulus E (kg / mm) of the cover glass substrate. ２ The film stress (kg / mm) is calculated by determining the Poisson's ratio Vs, thickness t (mm), and the thickness T (mm) of the polymerized hardened layer, and then applying these values ​​to the following formula. ２ Calculate the result. [Math 1]

12. A polymerizable composition according to claim 1 or 2, used in optical waveguides.

13. A polymerized cured product of the polymerizable composition according to claim 1 or 2.

14. A polymerized film comprising a polymerized cured product of the polymerizable composition according to claim 1 or 2.

15. A glass laminate comprising a polymerized cured product according to claim 13 and a glass substrate.

16. The glass laminate according to claim 15, wherein the thickness of the polymerized cured product is 50 to 500 μm.

17. The glass laminate according to claim 15, wherein the haze of the polymerized cured product is 0.1 to 1%.

18. The glass laminate according to claim 15, wherein the thickness of the glass substrate is 300 to 3000 μm.

19. The glass laminate according to claim 15, wherein the refractive index of the glass substrate is 1.6 to 2.

4.

20. The glass laminate according to claim 15, wherein the glass substrate comprises titanium oxide or niobium oxide.

21. A step of preparing the polymerizable composition according to claim 1 or 2, The following steps (i) and (ii); Step (i) After coating the polymerizable composition onto a substrate, a glass substrate is pressed onto the coated polymerizable composition to polymerize and cure the polymerizable composition. Step (ii) A step of coating the polymerizable composition onto a glass substrate, pressing a substrate against the polymerizable composition, and polymerizing and curing the polymerizable composition. At least one of the following steps, A method for manufacturing a glass laminate having the following characteristics.

22. The substrate has a pattern on the order of nanometers, A method for producing a glass laminate according to claim 21, wherein the obtained polymerized cured product has a nanoimprint structure.

23. The step of preparing the polymerizable composition is: A step of mixing the polythiol compound (A), a portion of the isocyanate compound (B), and the alkoxysilane compound (D) to obtain a prepolymer, A step of preparing a polymerization solution containing the remainder of the isocyanate compound (B), Includes, A method for producing a glass laminate according to claim 21, comprising mixing the prepolymer and the polymerization solution to obtain a polymerizable composition.

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