JP2012230309A - Stuck optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stuck optical component which has high heat resistance and transmittance, and has excellent antifouling properties, abrasion resistance and workability.SOLUTION: In the optical component formed by sticking a plurality of cured materials, the cured material contains an isocyanuric acid skeleton and a siloxane skeleton, the cured materials are stuck by using a composition containing the siloxane skeleton as an adhesive, and the optical component has a Shore D hardness of 50 or more and has a contact angle with respect to water of 60 degrees or more.

Description

The present invention relates to a bonded optical component having high heat resistance, high transmittance, excellent antifouling properties, and high hardness.

  Conventionally, camera modules have been widely used for mobile phone cameras and the like. The camera module includes a sensor unit that includes a light receiving element and a lens unit that combines one or more lenses.

  In recent years, for the purpose of downsizing / thinning and cost reduction, it is desired to increase the efficiency of the manufacturing process. As a method of manufacturing a small number of lenses, a wafer level lens array that has a configuration in which a plurality of lenses are formed on a substrate is manufactured, a plurality of lens arrays are bonded together, and a substrate unit is cut to mass-produce a lens unit. How to do is known.

  Furthermore, in order to increase the efficiency of the manufacturing process, a method of manufacturing a lens unit and a light receiving sensor unit in a batch by a solder reflow process is being introduced. In this method, a temperature history exceeding 250 ° C. may be applied, and high heat resistance is required for the lens unit.

  For example, Patent Document 1 describes a laminated lens using an addition-type silicone filler as an adhesive layer, but polycarbonate and polymethyl methacrylate are used as a lens material, and heat resistance is not sufficient.

  In addition, Patent Document 2 describes a manufacturing method for a lens array, but only describes that a thermosetting resin or a thermoplastic resin is used as a lens material. There was no description of the combination with the adhesive.

JP-A-5-19105 JP 2010-256563 A

  An object of the present invention is to provide a bonded optical component having high heat resistance, high transmittance, and excellent antifouling properties, friction resistance, and workability.

In view of the above circumstances, as a result of extensive studies by the present inventors, the present invention has the following configuration.
That is, the present invention has the following configuration.

  1) An optical component formed by laminating a plurality of cured products, wherein the cured product contains an isocyanuric acid skeleton and a siloxane skeleton, and the cured product is a composition containing a siloxane skeleton. An optical component characterized by using as an adhesive.

  2) The optical component according to 1), wherein the hardness of the optical component is 50 or more on Shore D.

  3) The optical component according to 1) or 2), wherein the light transmittance of the optical component is 70% or more at a wavelength of 400 nm.

  4) The optical component according to any one of 1) to 3), wherein the contact angle of the optical component with respect to water is 60 degrees or more.

  5) The optical component according to any one of 1) to 4), wherein the weight reduction rate of the adhesive is within 3% by heating at 260 ° C. for 10 minutes.

  6) The optical component according to any one of 1) to 5), wherein the adhesive further contains an isocyanuric acid skeleton.

  7) The optical component according to any one of 1) to 6), wherein the cured product has a refractive index of 1.400 to 1.550.

8) From (A) a compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) a compound containing at least two SiH groups in one molecule. The optical component according to any one of 1) to 7), wherein the optical component is a composition.

9) From a compound in which the cured product contains (C) at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, and (D) a compound containing at least two SiH groups in one molecule. The optical component according to any one of 1) to 8), wherein the composition is cured.

  10) The optical component according to any one of 1) to 9), wherein the composition used as an adhesive has a viscosity of 0.01 to 200 Pa · s.

  According to the present invention, it is possible to provide a bonded optical component that has high heat resistance, high transmittance, and excellent antifouling properties, friction resistance, and workability.

  Hereinafter, the present invention will be described in detail.

<Hardened product>
The cured product used in the optical component of the present invention is not particularly limited as long as it contains an isocyanuric acid skeleton and a siloxane skeleton. When the cured product contains an isocyanuric acid skeleton and a siloxane skeleton, an optical component excellent in heat resistance, transparency, friction resistance, and workability can be obtained.

  The plurality of cured products used in the present invention may be the same or different.

  The isocyanuric acid skeleton contained in the cured product is represented by the following general formula (I).

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an aryl group, and each R ¹ may be the same or different.) It is confirmed by analytical methods such as IR and NMR that the isocyanuric acid skeleton is contained. can do.

  The content of the isocyanuric acid skeleton contained in the cured product is preferably 5 to 50% by weight, and more preferably 10 to 45% by weight. When the content of the isocyanuric acid skeleton is in the range of 5 to 50% by weight, an optical component excellent in heat resistance and workability can be obtained. The content of the isocyanuric acid skeleton can be determined by quantifying the amide group derived from the isocyanuric acid skeleton by an analytical method such as NMR, mass spectrometry, or elemental analysis. The siloxane skeleton contained in the cured product is not particularly limited, and examples thereof include skeletons represented by the following general formula (II) and general formula (III).

(In the formula, each R ² and R ³ represents hydrogen or a monovalent organic group having 1 to 50 carbon atoms, and each R ² and R ³ may be the same or different. N is 1 to 1000. Represents the number of

(In the formula, each R ⁴ and R ⁵ represents hydrogen or a monovalent organic group having 1 to 50 carbon atoms, and each R ⁴ and R ⁵ may be the same or different. N is 2 to 10) Represents the number of
The inclusion of the siloxane skeleton can be confirmed by analytical methods such as IR and NMR.

  The content of the siloxane skeleton contained in the cured product is preferably 5 to 50% by weight, and more preferably 10 to 45% by weight. Here, the siloxane skeleton represents a Si—O bond. When the content of the siloxane skeleton is in the range of 5 to 50% by weight, an optical component excellent in heat resistance, transparency, and friction resistance can be obtained.

  The refractive index of the cured product is preferably in the range of 1.400 to 1.550 at 23 ° C. and 589 nm, more preferably in the range of 1.410 to 1.545, and 1.420 to 1.540. More preferably, it is in the range. If the refractive index at 589 nm is lower than 1.400, the thickness of the cured product becomes thick, making it difficult to reduce the thickness of the optical component, or increasing the curvature of the component, thereby reducing workability. On the other hand, if the refractive index is higher than 1.550, the reflectance at the interface increases, and the light transmittance may be reduced.

  The refractive index temperature dependency of the cured product is preferably −500 to 0 ppm, more preferably −400 to 0 ppm, and particularly preferably −300 to 0 ppm at a wavelength of 589 nm. When the refractive index temperature dependency is in the range of −500 to 0 ppm, a temperature range that can be used as an optical component is expanded.

Moreover, the contact angle of water with respect to the cured product is preferably 60 ° or more and 150 ° or less, more preferably 65 ° or more and 145 ° or less, and particularly preferably 70 ° or more and 130 ° or less. When the contact angle of water is in the range of 60 degrees or more and 150 degrees or less, the surface is hard to be damaged, and the cured product has good wettability when an adhesive is applied or when a coating agent such as an antireflection coating is applied to the surface. Can be obtained.
The cured product preferably has a linear expansion coefficient at 30 ° C. of 110 ppm / K or less, and more preferably 100 ppm / K or less. By reducing the linear expansion coefficient, it is possible to reduce the deviation of the focus and aberration due to the temperature of the optical component, and to reduce the thermal shock when a thermal history is applied when the component is fixed.

  The light transmittance of the cured product is preferably 75% or more and more preferably 80% or more at a wavelength of 400 nm. When the light transmittance is 75% or more, an optical component having a high transmittance can be obtained.

  The storage elastic modulus of the cured product at 50 ° C. is preferably 1000 MPa or more, more preferably 11000 MPa or more, and particularly preferably 1200 MPa or more. Here, the storage elastic modulus indicates an elastic modulus measured at a frequency of 1 Hz in a tensile mode, a compression mode, or a bending mode. By using a cured product having a storage elastic modulus of 100 MPa or more, an optical component having a small deformation with respect to stress can be obtained.

  The storage elastic modulus at 100 ° C. of the cured product is preferably 100 MPa or more, more preferably 200 MPa or more, and particularly preferably 500 MPa or more. By using a cured product having a storage elastic modulus of 100 MPa or more, an optical component excellent in heat distortion resistance can be obtained.

  The birefringence of the cured product is preferably 100 nm or less, more preferably 80 nm or less, and particularly preferably 50 nm or less. By using a cured product having a birefringence of 100 nm or less, an optical component with small aberration can be obtained. Here, birefringence represents a value measured by the parallel Nicols method.

  The curing method of the cured product is not particularly limited, but (C) a compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (D) at least SiH groups in one molecule. It is preferable to cure a composition comprising two compounds.

(C component)
The component (C) is not particularly limited as long as it is a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. For example, an organic compound, a silicone compound, an organic compound, and a silicone compound Examples of the compound are modified. The compound contained in the component (C) may be single or plural.
The carbon-carbon double bond contained in the component (C) is not particularly limited as long as it has reactivity with the SiH group, but the carbon-carbon double bond represented by the following general formula (IV) is reactive. From the point of view, it is preferable.

(In the formula, R ⁶ represents a hydrogen atom or a methyl group.) From the standpoint of availability of raw materials, R ⁶ is more preferably a hydrogen atom.
General formula (V) is suitable from the point that the heat resistance of hardened | cured material is high.

(In the formula, R ⁷ represents a hydrogen atom or a methyl group, and each R ⁷ may be the same or different.) From the viewpoint of easy availability of raw materials, R ⁷ is more preferably a hydrogen atom. .
The carbon-carbon double bond may be covalently bonded to the skeleton of the component (A) via a substituent, and the substituent is selected from C, H, N, O, S and halogen as constituent elements. Those containing only atoms are preferred. The following are mentioned as an example of a substituent.

  Two or more of these substituents may be connected by a covalent bond to form a substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Examples include oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and those shown below.

  From the viewpoint that heat resistance can be further improved, it is preferable that the carbon-carbon double bond having reactivity with the SiH group is contained in an amount of 0.1 mmol or more per 1 g of the component (C), and more preferably 0.5 mmol or more per 1 g. Those containing 1 mmol or more are particularly preferred.

  The number of carbon-carbon double bonds reactive with the SiH group of component (C) should be on average at least two per molecule, but it may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more. When the number of carbon-carbon double bonds that are reactive with the SiH group of component (C) is 1 or less per molecule, only a graft structure is formed even if it reacts with component (C). Don't be.

  From the viewpoint of high mechanical heat resistance and from the viewpoint of low stringiness of the raw material liquid and good moldability, handleability and filling properties, the component (C) preferably has a molecular weight of less than 900, and less than 700 Are more preferred, and those less than 500 are even more preferred.

  In order to obtain good workability, the component (C) preferably has a viscosity at 23 ° C. of less than 100 Pa · s, more preferably less than 50 Pa · s, and even more preferably less than 30 Pa · s. The viscosity here refers to a value measured by an E-type viscometer.

  As the component (C), those having a small content of a phenolic hydroxyl group and / or a compound having a derivative of a phenolic hydroxyl group are preferable from the viewpoint of suppressing coloring, particularly yellowing. What does not contain the compound which has a derivative is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  From the viewpoint of the refractive index and brittleness of the cured product, the component (C) is preferably an organic compound or a compound obtained by reacting an organic compound and a silicone compound, and particularly preferably an organic compound from the viewpoint of availability. From the viewpoint of heat resistance, a compound containing an isocyanuric acid skeleton represented by the following general formula (VI) is more preferable.

(Wherein R ⁸ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ⁸ may be different or the same).

As R < ⁸ > of the said general formula (VI), it is preferable that it is a C1-C30 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C3 20 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 10 carbon atoms are even more preferable. Examples of these preferable R ⁸ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like.

  Preferred examples of the compound represented by the above general formula (VI) include triallyl isocyanurate, trimethallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monophenyl isocyanate. And nurate, tris (2-acryloyloxyethyl) isocyanurate, and the like.

  From the viewpoint of high light resistance, the (C) component is preferably an alicyclic compound. Specific examples include vinylcyclohexene, dicyclopentadiene, 1,2,4-trivinylcyclohexane, vinyl norbornene, and the like.

(D component)
The component (D) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. A chain silicone compound, a cyclic silicone compound, a network silicone compound, a compound obtained by modifying an organic compound and a silicone compound Etc. are exemplified. (D) The compound contained in a component may be single or multiple.

  Specific examples of the chain polyorganosiloxane include the following general formula (VII)

(In the formula, each R ⁹ and R ¹⁰ represents hydrogen or a monovalent organic group having 1 to 50 carbon atoms, and each R ⁹ and R ¹⁰ may be different or the same, but at least 2 represents hydrogen, and n represents a number of 1 to 1000).
R ⁹ and R ¹⁰ are each preferably a monovalent organic group having 1 to 20 carbon atoms and monovalent having 1 to 15 carbon atoms from the viewpoint that the resulting cured product can have higher heat resistance. The organic group is more preferably a monovalent organic group having 1 to 10 carbon atoms. Examples of these preferable R ⁹ and R ¹⁰ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, vinyl group, allyl group, glycidyl group and the like. Can be mentioned.

  Examples of the cyclic polyorganosiloxane include the following general formula (VIII):

(Wherein R ¹¹ represents hydrogen or an organic group having 1 to 6 carbon atoms, and each R ¹¹ may be different or the same, but at least two are hydrogen. N is 2 to 10) And a cyclic polyorganosiloxane having at least two SiH groups in one molecule. R ¹¹ in the general formula (VIII) is preferably an organic group having 1 to 6 carbon atoms composed of C, H, and O, and more preferably a hydrocarbon group having 1 to 6 carbon atoms. preferable. R ¹¹ is particularly preferably a methyl group from the viewpoint of availability and heat resistance, and particularly preferably a phenyl group from the viewpoint of increasing the strength of the cured product. N is preferably a number of 3 to 10.

  Preferable specific examples of the cyclic polyorganosiloxane represented by the general formula (VIII) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7,9-pentamethylcyclopentasiloxane and the like.

  The molecular weight of the component (D) is not particularly limited, and any one can be suitably used. However, from the viewpoint that the fluidity of the curable composition can be more easily controlled, those having a low molecular weight are preferably used. In this case, the lower limit of the preferable molecular weight is 50, and the upper limit of the preferable molecular weight is 100,000, more preferably 10,000, and still more preferably 3000.

  From the viewpoint of having good compatibility with the component (C) and from the viewpoint that the problem of outgas from the composition that can lower the volatility of the component (D) is less likely to occur, the component (D) is a SiH group. An organic compound (D1) containing at least one carbon-carbon double bond having reactivity with a silicone compound (D2) having at least two SiH groups in one molecule; A compound that can be obtained is preferred.

((D1) component)
The component (D1) is an organic compound containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule. As the component (D1), the same component (D11) as the component (C) described above, which is the same as the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule is used. Can do. When the component (D11) is used, the cured product obtained has a high crosslink density and tends to be a cured product having a high mechanical strength.

  In addition, an organic compound (D12) containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used. When the component (D12) is used, the obtained cured product tends to have low elasticity.

  The bond position of the carbon-carbon double bond having reactivity with the SiH group of the component (D12) is not particularly limited, and may be present anywhere in the molecule. Further, the carbon-carbon double bond having reactivity with the SiH group of the component (D12) is not particularly limited, but the functional group described in the component (C) is preferable.

  The compound of the component (D12) can be classified into a polymer compound and a monomer compound, and each skeleton is preferably the skeleton explained in the component (C).

From the viewpoint of high heat discoloration, a compound containing an isocyanuric acid skeleton represented by the general formula (VI) described above is preferred as the component (D1).
From the viewpoint of high light resistance, the (D1) component is preferably an alicyclic compound. Specific examples include vinylcyclohexene, dicyclopentadiene, 1,2,4-trivinylcyclohexane, vinyl norbornene, and the like.
(D1) A component can be used individually or in mixture of 2 or more types.

((D2) component)
The component (D2) is not particularly limited as long as it is a polyorganosiloxane containing at least two SiH groups in one molecule. Specific examples of each compound include those described for the component (D).
(D2) A component can be used individually or in mixture of 2 or more types.

(Preliminary reaction)
(D1) reacting an organic compound containing at least one carbon-carbon double bond reactive with SiH group in one molecule and (D2) a silicone compound having at least two SiH groups in one molecule. The reaction for obtaining a compound containing at least two SiH groups in one molecule as component (D) will be described.

  The reaction method is not limited as long as (D1) and (D2) react to form a bond, and examples thereof include a thermal hydrosilylation reaction and a photohydrosilylation reaction.

  In the case of reacting the component (D1) and the component (D2), the mixing ratio of the component (D1) and the component (D2) is not particularly limited as long as two or more SiH groups remain in one molecule.

  Considering the strength of the resulting cured product, the number of moles (X) of carbon-carbon double bonds having reactivity with SiH groups in component (D1) and the number of moles of SiH groups in component (D2) The ratio with (Y) is preferably Y / X ≧ 2, and more preferably Y / X ≧ 3.

In the case of hydrosilylation, an appropriate catalyst may be used. As the catalyst, for example, platinum alone; a solid platinum supported on a support such as alumina, silica, carbon black; chloroplatinic acid; a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex _{(e.g., Pt (CH 2 = CH 2} ) 2 (PPh 3) 2, Pt (CH 2 = CH 2) 2 Cl 2); platinum - vinylsiloxane complex _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) a, Pt [(MeViSiO) ₄ ] _b ); platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ); platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt _{[P (OBu) 3] 4} ) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, a, b is an integer);. dicarbonyl dichloride It includes Karushuteto (Karstedt) _{catalyst, RhCl (PPh) 3, RhCl} 3, RhAl 2 O 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · 2H 2 O, NiCl 2, TiCl 4 and the like; platinum .

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the component (D2) in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ⁻¹⁰ mol, more preferably 10 ⁻⁸ mol, and the upper limit of the preferable addition amount is 10 ⁻¹ mol, more preferably 10 ⁻² mol, relative to 1 mol of SiH group of component (D2).

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

  Various methods can be used as a catalyst mixing method during the reaction, and a method in which a component (D1) mixed with a hydrosilylation catalyst is mixed with component (D2) is preferable. In some cases, it is difficult to control the reaction by a method in which a hydrosilylation catalyst is mixed with a mixture of the component (D1) and the component (D2). Further, in the method of mixing the component (D1) with the mixture of the component (D2) and the hydrosilylation catalyst, the component (D2) in the presence of the hydrosilylation catalyst has reactivity with the water mixed therein, and thus changes in quality. Sometimes.

  Although various reaction temperatures can be set, the lower limit of the preferred temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferred temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficient reaction tends to be long, and if the reaction temperature is high, it may be industrially disadvantageous. The reaction may be carried out at a constant temperature, and the temperature may be changed in multiple steps or continuously as required.

  Various reaction times and pressures during the reaction can be set as required. The reaction time is not particularly limited. From the economical aspect, it is preferably within 20 hours, more preferably within 10 hours. The pressure is not particularly limited, but is preferably from atmospheric pressure to 5 MPa, more preferably from atmospheric pressure to 2 MPa from the viewpoint that a special apparatus is required and the operation becomes complicated.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  The solvent and / or unreacted compound may be removed after the synthesis reaction. Examples of the removal method include vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 120 ° C, more preferably 100 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  In order to improve storage stability, storage at 10 ° C. or lower is preferable in an inert gas atmosphere such as nitrogen or argon, storage at 0 ° C. or lower is particularly preferable, and storage at −10 ° C. or lower is further preferable. .

  Examples of (D) obtained from the above reaction include a reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5,7-tetramethylcyclotetra Reaction product of siloxane, reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetra More preferred is a reaction product of methylcyclotetrasiloxane.

(Composition for obtaining a cured product)
The composition for obtaining the cured product of the present invention contains a suitable curing agent and curing catalyst. At this time, a hydrosilylation catalyst may be contained. Examples of suitable hydrosilyl catalysts and examples of the amount added include those described in the description of the component (D2).

The composition for obtaining the cured product of the present invention may contain a promoter. Examples of suitable promoters and addition amounts include those described in the description of component (D2).
You may add antioxidant to the composition for obtaining the hardened | cured material of this invention. Examples of the antioxidant include citric acid, phosphoric acid, sulfur-based antioxidant and the like, in addition to generally used antioxidants such as hindered phenols.

  Various types of hindered phenolic antioxidants such as Irganox 1010 available from BASF are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

Moreover, these antioxidants may be used alone or in combination of two or more.
A mold release agent may be added to the composition for obtaining the cured product of the present invention. The release agent is not particularly limited as long as it is compatible with the resin, does not impair the transparency of the cured product, and improves the release property from the mold. Examples of such a release agent include fluorine compounds, silicone compounds, and long chain hydrocarbon compounds. Examples of the fluorine-based compound include perfluoroalkyl-containing oligomers, perfluoroalkylethylene oxide, perfluoroalkenyl ethylene oxide, and the like. Examples of the silicone compound include dimethyl silicone and polyether-modified silicone having a reactive functional group such as a carbon-carbon double bond and SiH group. Examples of the long-chain hydrocarbon compound include stearic acid derivatives and palmitic acid derivatives.

  Moreover, these mold release agents may be used independently and may be used together 2 or more types.

  An ultraviolet absorber may be added to the composition for obtaining the cured product of the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.

Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.
An inorganic filler may be added to the composition for obtaining the cured product of the present invention. Addition of an inorganic filler is effective in increasing the strength of the material and improving flame retardancy. The inorganic filler is preferably a fine particle, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, barium sulfate, and a phosphor.

  As a method for adding the filler, for example, hydrolyzable silane monomers or oligomers such as alkoxysilane, acyloxysilane, and halogenated silane, metal alkoxides such as titanium and aluminum, acyloxide, or halides, and the like are cured according to the present invention. Examples thereof include a method in which an inorganic filler is produced in the composition by adding to the functional composition and reacting in the composition or a partial reaction product of the composition.

  The composition for obtaining the cured product of the present invention includes, in addition, ions such as a colorant, a storage stabilizer, a flame retardant, a flame retardant aid, a surfactant, an emulsifier, a leveling agent, a repellent, and antimony-bismuth. Trapping agent, thixotropic agent, ozone deterioration inhibitor, light stabilizer, thickener, antifoaming agent, plasticizer, reactive diluent, thermal stabilizer, conductivity enhancer, antistatic agent, radiation blocking agent Further, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity-imparting agent, a physical property adjusting agent and the like can be added within a range that does not impair the object and effect of the present invention.

(Method for producing cured product)
The method for producing a cured product in the present invention is not particularly limited as long as the curable composition described above is used, but it can be reacted by simply mixing each component, or reacted by irradiating light. It can also be reacted by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.

  Although various reaction temperatures can be set, the lower limit of the preferable temperature is 30 ° C, more preferably 60 ° C, and still more preferably 90 ° C. The upper limit of the preferable temperature is 300 ° C, more preferably 250 ° C, and still more preferably 200 ° C. When the reaction temperature is low, the reaction time for sufficient reaction is prolonged. If the reaction temperature is high, coloring or bulging may occur. If the reaction temperature is low, the reaction time for sufficient reaction tends to be long, and if the reaction temperature is high, coloring or bulging may occur.

  In order to produce the cured product of the present invention, any molding method can be used. The method for obtaining the cured product is not particularly limited, and examples thereof include generally known injection molding, press molding, compression molding, vacuum molding, transfer molding, extrusion molding, and cast molding. In particular, there are no restrictions on molding conditions such as speed and pressure at the time of material filling, and the mold temperature and curing time can be arbitrarily set.

  The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, it is preferable to carry out the reaction while raising the temperature in a multistage or continuous manner from the viewpoint that both workability during resin filling and shortening of the curing time can be achieved.

<Adhesive>
The adhesive used for the optical component of the present invention is not limited as long as it is a composition containing a siloxane skeleton. By containing a siloxane skeleton, an optical component having excellent heat resistance and transparency can be obtained.

  The viscosity of the composition used as the adhesive is preferably 0.01 to 200 Pa · s, more preferably 0.03 to 150 Pa · s, and even more preferably 0.05 to 120 Pa · s. . When the viscosity of the adhesive is lower than 0.01 Pa · s or higher than 200 Pa · s, workability when applying the adhesive may be lowered.

  The adhesive preferably does not color at high temperatures. In particular, when light is transmitted through the adhesive layer, coloring is a major issue. The colorability can be evaluated by, for example, the rate of decrease in light transmittance when heated at 260 ° C. for 10 minutes. The rate of decrease is preferably within 10%, more preferably within 8%. % Is particularly preferred.

  An adhesive that does not change in weight at high temperature is preferable. When the weight changes, for example, the alignment of the optical components bonded when passing through the solder reflow furnace may be shifted. The weight change can be evaluated by, for example, the weight change rate when heated at 260 ° C. for 10 minutes, the reduction rate is preferably within 3%, more preferably within 1%, more preferably 0.5% Is particularly preferred.

  The hardness of the adhesive layer contained in the optical component is preferably 50 or more on Shore A. If the hardness is low, the optical component may not withstand the stress during cutting and may be misaligned.

  The thickness of the adhesive layer contained in the optical component is preferably 0.01 to 2 mm, and more preferably 0.02 to 1 mm. When the thickness is in the range of 0.01 to 2 mm, an optical component with small thickness unevenness can be obtained.

  The method for curing the adhesive is not particularly limited, and examples thereof include hydrosilylation reaction, epoxy curing, and condensation reaction. Moreover, it is preferable to heat at the time of hardening or to irradiate light from a viewpoint of hardening time.

Pressure may be applied when the adhesive is cured. By applying pressure, the effect of suppressing sink marks and increasing the adhesive strength can be obtained.
The siloxane skeleton contained in the composition used as the adhesive is not particularly limited, and examples thereof include skeletons represented by the above general formula (II) and general formula (III).
The content of the siloxane skeleton contained in the adhesive is preferably 5 to 50% by weight, and more preferably 10 to 45% by weight. Here, the siloxane skeleton represents a Si—O bond. When the content of the siloxane skeleton is in the range of 5 to 50% by weight, an optical component excellent in heat resistance and transparency can be obtained.

  The composition used as the adhesive preferably contains an isocyanuric acid skeleton from the viewpoint of adhesiveness.

  The content of the isocyanuric acid skeleton contained in the adhesive is preferably 5 to 50% by weight, and more preferably 10 to 45% by weight. When the content of the isocyanuric acid skeleton is in the range of 5 to 50% by weight, an optical component excellent in heat resistance and adhesive strength can be obtained. The content of the isocyanuric acid skeleton can be determined by quantifying the amide group by an analysis method such as NMR, mass spectrometry, or elemental analysis.

The composition used as an adhesive is (A) a compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) containing at least two SiH groups in one molecule. A composition comprising the compound is preferred. When the composition comprising the component (A) and the component (B) is used, it is expected that the adhesive is cured quickly and the time for the bonding process is shortened.

  Here, the component (A) is not particularly limited as long as it is a compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. For example, the component described in the component (C) is used. Can be used.

The component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, those described in the component (D) can be used.
You may add an adhesion | attachment imparting agent to the composition used as an adhesive agent. In addition to commonly used adhesives as adhesion promoters, for example, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene- Examples include vinyl toluene copolymer, polyethylmethylstyrene, and aromatic polyisocyanate.

  The composition used as an adhesive may be used after being dissolved in a solvent. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, A halogen-based solvent such as 1,2-dichloroethane can be used.

<Optical parts>
The optical component in the present invention is an optical component obtained by bonding a plurality of the cured products described above with the adhesive described above.

  The hardness of the optical component of the present invention is preferably 50 or more on Shore D, more preferably 55 or more, and particularly preferably 60 or more. Here, Shore D is the hardness according to JIS K6253 type D durometer, and if the hardness by Shore D is high, there is mechanical strength, the surface is hardly scratched, and dust is not easily attached. Furthermore, since mechanical processing such as a cutter or a drill is possible, a complicated shape can be given or corrected after optical component molding.

  The light transmittance of the optical component of the present invention is preferably 70% or more at a wavelength of 400 nm, more preferably 75% or more, and particularly preferably 80% or more. When the light transmittance is 70% or more, light scattering is reduced, which is useful as an optical component.

  The contact angle of pure water with respect to the optical component of the present invention is preferably 60 degrees or more, more preferably 65 degrees or more, and particularly preferably 70 degrees or more. Here, the contact angle is a value measured at 23 ° C. using the θ / 2 method. An optical component having a water contact angle of 60 degrees or more has excellent antifouling properties and is useful as an optical component.

  The birefringence of the optical component is preferably 150 nm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less. By using a cured product having a birefringence of 150 nm or less, it is possible to obtain an effect that noise is reduced and an image becomes clear. Here, birefringence represents a value measured by the parallel Nicols method.

  The optical component is preferably excellent in solvent resistance. If the solvent resistance to solvents such as acetone, hexane, ethanol, isopropanol, and toluene is excellent, the range of solvent use during cleaning is widened, and optical components can be prevented from deteriorating during cleaning. The solvent resistance can be evaluated by immersing the sample in a solvent at room temperature for 48 hours and measuring the weight change rate of the sample. The weight change rate is preferably 10% or less, more preferably 8% or less, and more preferably 5%. Is particularly preferred.

  When producing the optical component of the present invention, it is preferable to wash the cured product which is an adherend before bonding. By washing the cured product, adhesion of foreign matters is reduced and the adhesive strength is increased. Examples of the cleaning method include gas injection of air or carbon dioxide, ultrasonic cleaning using alcohol or acetone, and the like.

  The method of bonding at the time of producing the optical component of the present invention is not particularly limited as long as the above-described cured product and adhesive are used, and the bonding is performed by any of point-like, linear, and planar methods at the time of bonding. An agent may be applied. As a method for applying the adhesive, for example, a coating method such as a dispensing method, a roll method, or a spray method can be used.

  The optical component of the present invention includes a light absorbing layer that absorbs light of an undesirable wavelength that causes deterioration of a cured product and an adhesive, and a transmission blocking layer that suppresses or prevents the transmission of reactive low molecules such as moisture and oxygen gas. Further, a layer such as an antiglare layer or an antireflection layer may be provided. As a coating method for these layers, a coating method such as a vacuum deposition method, a CVD method, a sputtering method, a dip coating method, or a spin coating method can be used.

  When bonding the cured product, a spacer having an arbitrary thickness may be used for adjusting the thickness of the adhesive layer.

  An optical component formed by bonding the cured product of the present invention with an adhesive can be mechanically processed. By performing mechanical processing, it is possible to give or correct a complicated shape to the optical component.

  Applications of the optical component of the present invention include, for example, camera lenses such as (digital) cameras, mobile phones, and in-vehicle cameras, optical lenses such as projection lenses, f-θ lenses, and pickup lenses, optical films, optical sheets, and light guides. Roadway, dicing tape, insulating materials (including printed circuit boards, wire coatings, etc.), high-voltage insulating materials, molding materials (including sheets, films, FRP, etc.), stereolithography, solar cell materials, display materials, recording materials It can be applied to photosensitive drums for copying machines.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Synthesis Example 1)
Into a 2 L autoclave, 650 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 600 g of toluene were added, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 90 g of triallyl isocyanurate, 110 g of toluene and 3.5 g of a xylene solution of platinum vinylsiloxane complex (containing 0.03 wt% as platinum) was added in 10 divided portions. After 6 hours of heating and stirring from the end of dropping, ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more, and the reaction was terminated by cooling. The reaction was terminated by cooling.

Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were devolatilized under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a colorless and transparent liquid. ^{According to 1} H-NMR, this product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of triallyl isocyanurate (referred to as (α1). Although it was a mixture, it was found that it contains the following compounds containing 9 SiH groups in one molecule as the main component).

(Synthesis Example 2)
A magnetic stirring bar, a condenser tube, and a dropping funnel were set in a 2 L four-necked flask. Into this flask, 590 g of 1,3,5,7-tetramethylcyclotetrasiloxane (intramolecular SiH number 4) and 550 g of toluene were placed, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 100 ° C. A mixed solution of 130 g of diallyl monoglycidyl isocyanurate (number of double bonds in the molecule) 130 g, toluene 130 g and platinum vinylsiloxane complex xylene solution (containing 0.03 wt% as platinum) was added in 10 divided portions. . After stirring for 3 hours from the end of dropping, the reaction was terminated by cooling.

Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were devolatilized under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a colorless and transparent liquid. ^{According to 1} H-NMR, this is a product obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of diallylmonoglycidyl isocyanurate (referred to as (α2). Is a mixture but contains the following compounds containing 6 SiH groups in one molecule as a main component).

(Hardened material creation examples 1 and 2)
The composition was adjusted with the blending composition (β1, β2) shown in Table 1. In the adjustment method, the component (C) and the catalyst were mixed, and the mixture of the component (D) and the cocatalyst was further added thereto, followed by stirring and degassing to obtain a composition.

  Next, the obtained composition is poured into a cell prepared by sandwiching a 1 mm-thick silicone rubber sheet as a spacer between two glass plates, and heated in a hot air oven at 120 ° C. for 40 minutes and 180 ° C. for 30 minutes. A plate-like cured product (β1, β2) was obtained.

(Comparative example of cured product creation)
The composition was adjusted with the composition shown in Table 1 (epoxy resin).

  Next, the obtained composition is poured into a cell prepared by sandwiching a 1 mm thick silicone rubber sheet as a spacer between two glass plates, and heated in a hot air oven at 150 ° C. for 12 hours to form a plate-like cured product (Epoxy resin) was obtained.

(Adhesive preparation example)
The composition was adjusted with the formulation shown in Table 1. In the adjustment method, the component (A) and the catalyst were mixed, and the mixture of the component (B) and the cocatalyst was added and stirred and degassed to obtain a composition (γ1).

(Examples 1 and 2)
A cured product and an adhesive were bonded together in the combinations shown in Table 2 to obtain an optical component. In the laminating method, a 0.5 mm thick spacer was placed on the cured product, the adhesive composition was applied, and the cured product was further covered from above to sandwich the adhesive. This was heated in a hot air oven at 150 ° C. for 12 hours to cure the adhesive and obtain a bonded optical component.

(Comparative Example 1)
A cured product and an adhesive were bonded together in the combinations shown in Table 2 to obtain an optical component. An epoxy resin (ME-540 / HV-540) manufactured by Pernox Corporation was used as an adhesive. The bonding method was the same as in Examples 1 and 2.

(Measurement, test)
(Light transmittance)
The optical transmittance and YI at 400 nm of the obtained optical component were measured with a spectrophotometer (U-3300, Hitachi).

(Optical component heat resistance test)
The optical component was heated in a hot air oven at 260 ° C. for 10 minutes. About the optical component after a heat resistance test, the light transmittance of 400 nm was measured (transmittance after a heat resistance test), and the numerical value was derived | led-out according to the following formula. Here, the “initial transmittance” is the light transmittance at 400 nm of the optical component before the heat resistance test.
“Light transmittance decrease rate” = (1− “Transmittance after heat resistance test” / “Initial transmittance”) × 100
(hardness)
The optical component was placed on the glass, and the hardness was measured with a type D durometer according to JIS K6253.

(Contact angle)
It measured using Kyowa Interface Chemical Co., Ltd. contact angle meter S-150. Pure water (φ2 mm) was used as a solvent, and the measurement was performed by the θ / 2 method.

(Refractive index)
The refractive index at 404, 594, and 827 nm was measured using a prism coupler 2010 / M manufactured by Metatronic. The refractive index at 589 nm was determined by Cauchy's approximation formula of the built-in software.

(Storage modulus)
Using a dynamic viscoelastic device DVA-200 manufactured by IT Measurement Control Co., Ltd., measurement temperature room temperature to 200 ° C., heating rate 5 ° C./min, strain 0.1%, frequency 10 Hz, chuck distance 20 mm, in tension mode It was measured.

(Adhesive heat resistance test)
The obtained composition is poured into a cell prepared by sandwiching a 1 mm thick silicone rubber sheet as a spacer between two glass plates, and heated in a hot air oven at 150 ° C. for 12 hours to obtain a cured adhesive. Got. The cured adhesive was cut into 1 cm square and weighed (initial weight). The cured adhesive was heated in a hot air oven at 260 ° C. for 10 minutes, the weight after removal was measured (weight after heat resistance test), and a numerical value was derived according to the following formula.
“Weight reduction rate” = “weight after heat resistance test” / “initial weight” × 100
<Viscosity>
Using an EHD viscometer manufactured by Tokyo Keiki Co., Ltd., a 23 ° C. viscosity was measured using an EHD type 1 ° 34 ′ × R24 cone.

  As shown in Table 2, it can be seen that the bonded optical component having the characteristics of the present invention has a low heat transmittance, a low light transmittance decrease rate after a heat test, and a high hardness.

Claims (10)

  An optical component formed by laminating a plurality of cured products, wherein the cured product contains an isocyanuric acid skeleton and a siloxane skeleton, and a composition containing a siloxane skeleton is bonded to the cured product. An optical component that is used as an agent.   The optical component according to claim 1, wherein the hardness of the optical component is 50 or more in Shore D.   The optical component according to claim 1 or 2, wherein the optical component has a light transmittance of 70% or more at a wavelength of 400 nm. The optical component according to any one of claims 1 to 3, wherein a contact angle of the optical component with respect to water is 60 degrees or more.   The optical component according to any one of claims 1 to 4, wherein a weight reduction rate of the adhesive is within 3% by heating at 260 ° C for 10 minutes. The optical component according to any one of claims 1 to 5, wherein the adhesive further contains an isocyanuric acid skeleton. The optical component according to claim 1, wherein the cured product has a refractive index of 1.400 to 1.550. The composition in which the adhesive comprises (A) a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, and (B) a compound containing at least two SiH groups in one molecule. The optical component according to claim 1, wherein the optical component is a product. The cured product comprises (C) a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, and (D) a composition comprising a compound containing at least two SiH groups in one molecule. The optical component according to any one of claims 1 to 8, wherein the optical component is cured.   The viscosity of the composition used as an adhesive agent is 0.01-200 Pa.s, The optical component as described in any one of Claims 1-9 characterized by the above-mentioned.