JP2003335823A - Polymerizable composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition useful as a component of an adhesive, a coating material, ink, coating and the like, a cured product obtained by curing this polymerizable composition, and furthermore an optical sheet and an optical plastic member which use the cured product. <P>SOLUTION: The polymerizable composition has an alicylic skeleton- containing bis(meth)acrylate äe.g. bis(hydroxymethyl)tricyclo[5.2.1.0<SP>2</SP>,<SP>6</SP>]decane = dimethacrylate} and an alicyclic skeleton-containing mono(meth)acrylate having a carboxy group äe.g. bis(hydroxymethyl)tricyclo[5.2.1.0<SP>2</SP>,<SP>6</SP>]decane = β-carboxy propionate methacrylate}. The adhesive, coating material, ink, and coating contain the polymerizable composition, and the cured product is obtained by polymerizing the polymerizable composition, and the optical sheet and optical plastic member have the cured product. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerizable composition containing an alicyclic skeleton bis (meth) acrylate and an alicyclic skeleton mono (meth) acrylate, and more specifically to an adhesive, It is useful as a component of coating agents, inks, paints, etc., and when it is cured, it is a polymerizable composition suitable for optical sheets, optical plastic members, etc., cured products, and various applications using them. It is about.

[0002]

2. Description of the Related Art Conventionally, a photocurable member has a shorter curing time than a thermosetting member, an improvement in productivity due to a shorter manufacturing time, and a function that can be achieved only by photocuring. It is used for optical plastic members. However, conventional photocurable members have poor transparency when used for optical applications, and when exposed to a high temperature environment after bonding, optical properties such as coloring deteriorate. Further, it has been pointed out that a photocurable member having heat resistance has insufficient adhesiveness.

As a photocurable member having heat resistance and transparency, for example, JP-A-9-152510 and JP-A-200 can be used.
No. 1,342,222 discloses tricyclo [5.2.1.0].
^A curable member composed of a resin obtained by polymerizing and curing a composition composed of a bis (meth) acrylate compound substituted at the 3,8 (or 3,9 or 4,8) position of a ^2,6 ] decane skeleton and a mercapto compound has been proposed. However, this resin has a bending adhesive strength (S _A ) according to JIS K6856 of 0.1 or less, and there is a problem that the adhesiveness is insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a cured product which can be used for a curable plastic member having excellent adhesiveness, and a polymerizable composition which provides such a cured product. The purpose is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by using a polymerizable composition containing a mono (meth) acrylate compound having a carboxyl group, The inventors have found that a cured product having excellent adhesiveness can be obtained, and completed the present invention. That is, by incorporating a carboxyl group-containing component whose structure and properties are similar to those of the polymer into the crosslinked polymer structure, the adhesiveness can be improved without deteriorating the properties such as heat resistance. , Is.

That is, the gist of the present invention is: 1. A polymerizable composition containing the following components A and B. Component A: Bis (meth) aliphatic ring skeleton represented by the following formula (I)
Acrylate

[0007]

[Chemical 3]

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, m represents 1 or 2, and n
Represents 0 or 1, and p and q are each independently 0,
Indicates 1 or 2. ) Component B: alicyclic skeleton mono (meta) represented by the following formula (II)
Acrylate

[0009]

[Chemical 4]

(In the formula, R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a divalent hydrocarbon residue, m represents 1 or 2, n represents 0 or 1, and r and s Each independently represent 0, 1 or 2.) Adhesives, coating agents, inks, paints containing the polymerizable composition of 2,1 and by polymerizing the polymerizable composition of 3,1 Which is a cured product, an optical sheet having a cured product of 4, 3, and an optical plastic member.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polymerizable composition of the present invention comprises the following component A and component B. The alicyclic skeleton bis (meth) acrylate represented by the formula (I) constituting the component A (hereinafter, referred to as
Specific examples of bis (meth) acrylate may be abbreviated), for example, bis (hydroxy) tricyclo [5.
2.1.0 ^2,6 ] decane = diacrylate, bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate, bis (hydroxy) tricyclo [5.2.
1.0 ^2,6 ] decane acrylate methacrylate and mixtures thereof, bis (hydroxy) pentacyclo [6.
5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] Pentadecane = diacrylate, bis (hydroxy) pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane dimethacrylate, bis (hydroxy) pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] Pentadecane acrylate methacrylate and mixtures thereof, and the like.

Of these, bis (hydroxymethyl)
Tricyclo [5.2.1.0 ^2,6 ] decane diacrylate, bis (hydroxymethyl) tricyclo [5.2.
1.0 ^{2, 6]} decane = dimethacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2, 6]} decane = acrylate methacrylate and mixtures thereof are preferred.

These bis (meth) acrylates may be used alone or in combination of two or more. The proportion of bis (meth) acrylate in the polymerizable composition of the present invention is not particularly limited, but is 10 to 90 relative to 100 parts by weight of the total of the component A and the component B.
It is preferably part by weight, more preferably 20 to 8
The amount is 0 parts by weight, more preferably 30 to 70 parts by weight.

The method for producing bis (meth) acrylate is not particularly limited, and a general ester synthesis method (edited by the Chemical Society of Japan, New Experimental Chemistry Course, 14, Synthesis and Reaction of Organic Compounds (II)) Maruzen, 1977) etc., but as a typical production method, (i) an alicyclic skeleton diol represented by the formula (III) (hereinafter referred to as a diol of the formula (III) or a diol Abbreviated) and a (meth) acrylic acid esterification reaction (JP-A-62-225508),

[0015]

[Chemical 5]

(Wherein, m is 1 or 2, n is 0 or 1, and p and q are independently 0, 1 or 2
Indicates. ) (Ii) A method by a transesterification reaction between a diol and a (meth) acrylic acid ester, (iii) a method by a reaction between a diol and a (meth) acrylic acid halide, and the like. Among these, the methods (i) and (ii) are practical and preferable.

In the esterification reaction of the diol (i) with the (meth) acrylic acid, usually 2.0 to 2.6 mol of (meth) acrylic acid is used with respect to 1 mol of the diol. Sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, p-
Using toluene sulfonic acid, benzene sulfonic acid, cation-type ion exchange resin, etc., it is usually carried out in the presence of a solvent such as toluene, benzene, heptane, hexane, etc., while distilling off water produced by the reaction. As specific examples of the diol of formula (III) are for example bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6] decane, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^{3 , 6} . 0 ^2,7 .
0 ^9,13 ] Pentadecane and the like can be mentioned. Among these, bis (hydroxymethyl) tricyclo [5.2.
1.0 ^2,6 ] decane is commercially available as “TCD alcohol DM (trade name of Celanese Co.)”.

In the transesterification reaction of the diol (ii) with the (meth) acrylic acid ester, the (meth) acrylic acid ester is generally added in an amount of 2.0 to 10.0 with respect to 1 mol of the diol. Mole is used as the catalyst, for example, sulfuric acid, p-toluenesulfonic acid, tetrabutyl titanate, tetraisopropyl titanate, potassium butoxide, etc., and methanol produced by the reaction in the presence of a solvent such as toluene, benzene, heptane, and hexane is usually used. Do it while distilling off. In the reaction, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, copper salt or the like can be used as a polymerization inhibitor.

In these reactions, the progress of the reaction was analyzed by high performance liquid chromatography, etc.
The reaction mixture was stopped before the completion of 0%, and unreacted diol, (meth) acrylic acid, catalyst, polymerization inhibitor,
A mixture of bis (meth) acrylate and mono (meth) acrylate can be obtained by removing the solvent and the like.

A material having an appropriate mixing ratio can be used as it is as a raw material for a mixture of the components A and B of the photocurable composition of the present invention. In the component B which is the other constituent component in the present invention, the divalent hydrocarbon residue defined by R ₄ is an ethylene group, a vinylene group, a trimethylene group, an o-phenylene group, a 1,2-cyclohexylene group. Etc., and those having 8 or less carbon atoms are preferable. Further, the divalent hydrocarbon residue may have a substituent such as a carboxyl group, a hydroxyl group and a sulfo group.

The component B which constitutes the component B is represented by the formula (II).
Alicyclic skeleton mono (meth) acrylate (hereinafter referred to as mono (meth)
A) may be abbreviated as acrylate)
Bis (hydroxy) tricyclo [5.2.1.0]
^2,6] Decane = monoacrylate, bis (hydroxy) to
Ricyclo [5.2.1.0]^2,6] Decane = Monomethacry
Bis (hydroxy) tricyclo [5.2.1.0]
^2,6] Decane acrylate methacrylate and these
Mixture, bis (hydroxy) pentacyclo [6.5.
1.1^3,6． 0^2,7． 0^9,13] Pentadecane = Monoacry
Rate, bis (hydroxy) pentacyclo [6.5.
1.1^3,6． 0^2,7． 0^9,13] Pentadecane = monomethac
Relate, bis (hydroxy) pentacyclo [6.5.
1.1^3,6． 0 ^2,7． 0^9,13] Pentadecane = Ackley
Hydroxyl groups such as tomethacrylate and their mixtures
Mono (meth) acrylate compound and succinic anhydride, no
Maleic acid water, glutaric anhydride, 3-methylgluta anhydride
Polycarboxylic acid such as acid, phthalic anhydride, trimellitic anhydride
Examples include reaction products of boric acid with an intramolecular acid anhydride.

Of these, bis (hydroxymethyl)
Tricyclo [5.2.1.0 ^2,6 ] decane = monoacrylate, bis (hydroxymethyl) tricyclo [5.2.
The reaction product of 1.0 ^2,6 ] decane monomethacrylate or a mixture thereof with succinic anhydride or glutaric anhydride is preferable. These mono (meth) acrylates may be used alone or in combination of two or more.

The proportion of mono (meth) acrylate in the polymerizable composition of the present invention is not particularly limited, but the component A
It is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, and further preferably 30 to 70 parts by weight, based on 100 parts by weight of the total of the component B and the component B. If the proportion of mono (meth) acrylate is too small, the effect of improving the adhesiveness cannot be obtained, and conversely, if it is too large, the heat resistance of the cured resin may decrease.

The carboxyl group-containing mono (meth) acrylate can be synthesized by half-esterifying the hydroxyl group of the hydroxyl group-containing mono (meth) acrylate compound with an intramolecular acid anhydride. The half-esterification reaction can be synthesized by reacting a hydroxyl group of a hydroxyl group-containing mono (meth) acrylate compound with an equivalent amount of an intramolecular acid anhydride without a catalyst or in the presence of a catalyst such as a tertiary amine such as triethylamine or pyridine.

Here, the hydroxyl group-containing mono (meth) acrylate is produced as a precursor when the above-mentioned bis (meth) acrylate is produced, and has a (meth) acryloyl group at one terminal of the molecule, It is a compound having a hydroxyl group at the other end. Specifically, a method for synthesizing the above-mentioned bis (meth) acrylate of the formula (I), for example (i),
In the method (ii) or (iii), the amount of (meth) acrylic acid, (meth) acrylic acid ester, or (meth) acrylic acid halide used per 1 mol of the diol is reduced, or the reaction proceeds 100%. By stopping the reaction in the previous step, it is possible to obtain a mixture containing bis (meth) acrylate and mono (meth) acrylate in a desired ratio. If necessary, the raw material diol to be mixed can be removed by washing using the difference in solubility, recovered, and used for the next reaction, which is convenient.

Since the chemical structure of this mono (meth) acrylate is similar to that of bis (meth) acrylate, the polymerization rate is almost equal to that of bis (meth) acrylate, which causes an increase in birefringence during polymerization and curing. There is no point. Further, since it has an alicyclic skeleton similar to that of a specific bismethacrylate, there is little influence such as reduction in heat resistance. The polymerizable composition of the present invention may contain auxiliary components other than the component A and the component B as long as the gist of the present invention is not impaired. As auxiliary components, monomers other than radically polymerizable component A and component B, chain transfer agents such as mercaptan compounds, antioxidants, ultraviolet absorbers, ultraviolet stabilizers, dyes and pigments, fillers, silane coupling agents And so on. Among these, it is preferable in the present invention to contain a silane coupling agent.

Examples of the monomer other than the radically polymerizable component A and component B include methyl methacrylate and 2-
Hydroxyethyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 2,2-bis [4- (β-
Methacryloyloxyethoxy) phenyl] propane,
Methacrylate compounds such as 2,2-bis [4- (β-methacryloyloxyethoxy) cyclohexyl] propane, 1,4-bis (methacryloyloxymethyl) cyclohexane and trimethylolpropane trimethacrylate; styrene, chlorostyrene, divinylbenzene,
Examples thereof include styrene compounds such as α-methylstyrene; acrylic acid derivatives such as acrylamide, methacrylamide, acrylonitrile and methacrylonitrile.
Among these, 2,2-bis [4- (β-methacryloyloxyethoxy) phenyl] propane, 2,2-bis
Particularly preferred are [4- (β-methacryloyloxyethoxy) cyclohexyl] propane, 1,4-bis (methacryloyloxymethyl) cyclohexane, trimethylolpropane trimethacrylate, and mixtures thereof. The radical-polymerizable monomer is usually added in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the components A and B.

As the chain transfer agent, for example, a polyfunctional mercaptan compound having two or more molecule thiol groups in the molecule may be used, and by using the polyfunctional mercaptan compound in combination, a suitable cured product can be obtained. It can impart toughness. Examples of the mercaptan compound include pentaerythritol tetrakis (β-thiopropionate), pentaerythritol tetrakis (β-thioglycolate), trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (β
-Thioglycolate), diethylene glycol bis (β
-Thiopropionate), diethylene glycol bis (β-thioglycolate, dipentaerythritol hexakis (β-thiopropionate), dipentaerythritol hexakis (β-thioglycolate), etc.
Valent thioglycolate or thiopropionate; tris [2- (β-thiopropionyloxy)
Ethyl] triisocyanurate, Tris [2- (β-thioglyconyloxy) ethyl] triisocyanurate, Tris [2- (β-thiopropionyloxyethoxy) ethyl] triisocyanurate, Tris [2- (β-thio Ω-SH such as glyconyloxyethoxy) ethyl] triisocyanurate, tris [2- (β-thiopropionyloxy) propyl] triisocyanurate, tris [2- (β-thioglyconyloxy) propyl] triisocyanurate Group-containing triisocyanurate; α, ω-SH group-containing compounds such as benzene dimercaptan, xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and the like. Among these, pentaerythritol tetrakis (β-thiopropionate), trimethylolpropane tris (β-thiopropionate),
Tris [2- (β-thiopropionyloxyethoxy)
Ethyl] triisocyanurate and mixtures thereof are especially preferred. The mercaptan compound is usually added in a proportion of 30 parts by weight or less based on 100 parts by weight of the total of the components A and B.

As the silane coupling agent, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, β- (3, 4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropylmethyldimethoxysilane, γ-
Aminopropyltrimethoxysilane, N-phenyl-γ
-Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like can be mentioned. Among them, γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, γ- (methacryloxypropyl) methyldiethoxysilane, γ-
(Methacryloxypropyl) triethoxysilane, γ-
(Acryloxypropyl) trimethoxysilane and the like have methacryl or acryl groups in the molecule and can be copolymerized with the compositions A and B of the present invention, and thus are preferably used. The weight ratio is as follows: component A and component B
It is usually 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight in total. If the amount is less than 0.1 parts by weight, a sufficient effect cannot be obtained, and if the amount is more than 50 parts by weight, optical properties such as transparency may be impaired.

The polymerizable composition of the present invention can be polymerized and cured by a known method to give a cured product. Specifically, a method in which a thermal polymerization initiator that generates a radical by heating is added to the polymerizable composition in advance and the mixture is heated to polymerize (hereinafter sometimes referred to as “thermal polymerization”), and the polymerizable composition is prepared in advance. Initiation of radical polymerization, such as a method in which a photopolymerization initiator that generates radicals due to active energy rays such as ultraviolet rays is added to an object and polymerization is performed by irradiating with active energy rays (hereinafter sometimes referred to as "photopolymerization"). Examples of the method include a method in which an agent is added in advance and polymerization is performed, and photopolymerization is more preferable in the present invention.

Specific examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxy carbonate, t-butyl peroxy (2-ethyl hexanoate) and the like. Specific examples of the photopolymerization initiator include:
Benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-
Hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned. Preferred are 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzophenone.

Even if these polymerization initiators are used alone, 2
You may use together 1 or more types. The amount of the photopolymerization initiator added is usually 0.1 part with respect to the total of 100 parts by weight of the component A and the component B.
The amount is 01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. If the amount of the photopolymerization initiator added is too large, not only the polymerization will rapidly proceed and the birefringence will increase, but also the hue may deteriorate. On the other hand, if the amount is too small, the composition may not be sufficiently polymerized.

The amount of active energy rays to be irradiated is arbitrary as long as the photopolymerization initiator generates radicals, but when the amount is extremely small, the heat resistance and mechanical properties of the cured product are poor because the polymerization is incomplete. If it is not sufficiently expressed, and on the contrary, if it is excessively excessive, deterioration due to light such as yellowing of the cured product may occur. Therefore, UV of 200 to 400 nm is preferable in accordance with the composition of the monomer and the type and amount of the photopolymerization initiator. Is 0.1-20
Irradiate in the range of 0 J / cm ² . It is more preferable to divide the active energy ray into a plurality of times for irradiation. Ie 1
Irradiating about 1/20 to 1/3 of the total irradiation amount for the second time and irradiating the necessary remaining amount for the second time and thereafter, a cured product having smaller birefringence can be obtained. Specific examples of the lamp to be used include a metal halide lamp and a high pressure mercury lamp.

For the purpose of promptly completing the curing by polymerization, photopolymerization and thermal polymerization may be carried out simultaneously. Specifically, the polymerizable composition and the entire mold are heated in the range of 30 to 300 ° C. at the same time as the irradiation with the active energy ray to cure the composition.
In this case, a thermal polymerization initiator may be added to the polymerizable composition in order to complete the polymerization, but if a large amount is added, the birefringence of the cured product increases and the hue deteriorates. The amount of the agent added is 0.1 to 2 parts by weight, preferably 0.3 to 1 part by weight, based on 100 parts by weight of the total of the components A and B.

After the photopolymerization, the obtained cured product may be heated. Thereby, the completion of the polymerization reaction and the internal strain generated during the polymerization can be reduced. The heating temperature is appropriately selected according to the composition of the cured product and the glass transition temperature, but is usually preferably around the glass transition temperature or lower. If the heating temperature is too high, the hue of the cured product may deteriorate.

The polymerizable composition of the present invention is preferably used as an adhesive as described below, but is not limited thereto unless it goes against the gist of the present invention. When the polymerizable composition of the present invention is used as an adhesive, various adherends can be used. For example, metal, metal oxide, glass,
Examples include paper, wood, plastic sheets, and plastic films. Of these, glass and transparent plastic are preferably used for this purpose. The glass may be a plate material or a structure. Further, the surface of the plastic sheet or film may be made of glass by vapor deposition, sputtering or the like.

Specifically, first, in order to remove deposits such as fats and oils on the surface of glass having a smooth surface, clean it with a cotton cloth moistened with methanol or industrial alcohol, and adhere until the odor of the solvent disappears from the surface. Dry side up.
If necessary, the glass surface can be treated with a primer. Next, a predetermined amount of the component A and the component B of the present invention, a photopolymerization initiator, and various auxiliary components are mixed, and an adhesive is applied to the glass surface in a predetermined amount. An example of the coating method will be described below. A method of dropping a predetermined amount, a method of applying an adhesive to a predetermined thickness using a spin coater when it is necessary to control the adhesive thickness, and a method of applying the above to the adhesive solution when adhering to both sides. Dip the glass plate,
A method to apply the adhesive liquid uniformly by pulling it up at a constant speed, a bar coat method in which a predetermined amount is dropped and then the surface is wiped with a plate having a certain gap, and transparent particles with a certain size are mixed to bond It may be applied by a method of making the thickness constant, a method of applying a spacer having a constant thickness on the outside of the adhesive surface, or the like.

After applying the adhesive by the above method, the glass plates are attached. Various bonding methods can be adopted as long as they do not violate the spirit of the present invention. For example,
The glass plate on the side to be covered is installed at an angle, and the method of laminating the glass is gradually reduced so that air does not enter inside, the method of laminating in vacuum, the method of gradually laminating while bending the glass, etc. . If necessary, they can be left together after being attached.

Next, by exposing to active energy rays
Cure the adhesive. The curing is done by the above-mentioned ultraviolet rays, etc.
Of photopolymerization to generate radicals by active energy rays
It is carried out by a known radical polymerization in which an initiator is added. The present invention
In, the light transmittance is one of the important factors. In particular
Transparency in the visible light region is required. With a wavelength of 500 nm
A monochromatic light having a transmittance of 80% or more is preferably used.
To be More preferably, it is 85% or more. 8 transmittance
If it is less than 0%, it is incident when used for optical applications.
The ratio of the emitted light to the light is small and only dark emitted light can be obtained.
This is a problem. Also, as the strength of adhesion, JIS-K6
Bending test in 856, force per unit area
(S_AValue) is 0.1 N / mm ²Those with the above strength are suitable
Used for. 0.1 N / mm²Less than
The adhesive surface peels off with a slight force, and an air layer forms at the peeled interface.
If so, reflection may occur and the light transmittance may decrease.
It Also, there is a possibility that it physically peels off and falls off,
0.1 N / mm²More is needed. The upper limit is specifically stated
However, if it is attached to a glass plate, use an adherend
If we can obtain the adhesive strength until a certain glass plate breaks
Yes.

The polymerizable composition of the present invention can be used as various coating agents, inks and paints in addition to adhesives. The cured product obtained by curing the curable composition of the present invention can be used as a photocurable member suitable for optical sheets, optical plastic members and the like.

[0041]

EXAMPLES The following examples serve to explain the present invention more specifically. In addition, the part in an example shows a weight part. The physical properties of the cured product described in the examples were measured by the following test methods. (1) Adhesiveness test method Adhesiveness test method was performed according to JIS-K6856. Thickness 1.6mm, length 100mm, width 2
The surface of a 5 mm glass plate was wiped off with a gauze soaked with methanol, dried at room temperature until the odor disappeared, and two glass plates were pasted together with an adhesion margin of 12.5 mm. See FIG. After that, using a support made of the same material as the glass plate, a test piece was set as shown in FIG. The adhesive strength was determined by the following formula from the maximum load when the load part was moved at 10 mm / min and the area of the overlapping part of the test piece.

[0042]

[Formula 1] S _A = P / A S _A : Flexural adhesive strength (N / mm ² ) P: Maximum load (N) A: Area of the measured overlapping portion of the test piece (m
m ² ) Moreover, the state of destruction was classified as follows according to the description of JIS-K6856. Adhesive failure (AF), cohesive failure (C
F), Destruction of adherend (MF) (2) Cross-cut peeling test The adhesion test was carried out in accordance with JIS-K5400-8.5.1. The case where there was no peeling was 10 points, and the case where the peeled area was 65% or more of the total square area was 0 point. (3) Light transmittance The light transmittance was calculated by irradiating the bonded portion of the sample with monochromatic light having a wavelength of 500 nm and using the following formula.

[0043]

## EQU2 ## T = (I ₁ / I ₀ ) × 100 T: Light transmittance (%) I ₁ : Transmitted light intensity I ₀ : Incident light intensity

Example 1 Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 50 parts by weight, bis (hydroxymethyl) tricyclo
[5.2.1.0 ^2,6 ] decane = β-carboxyl propionate methacrylate ² parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photoinitiator based on 100 parts by weight of a mixture of 50 parts by weight. The parts were mixed and stirred at 60 ° C. until uniform. This was called a monomer mixture. Thickness 1.6 mm, length 100 m
The surface of a glass plate having a width of 25 mm and a width of 25 mm was wiped with a gauze soaked with methanol, dried at room temperature until the odor disappeared, and then a few drops of the above-mentioned monomer mixture liquid was dropped, and the adhesive margin was set to 12.5 mm. The glass plates were stuck together. Ultraviolet rays were irradiated for 5 minutes under a metal halide lamp having an output of 40 W / cm, which was located at a distance of 40 cm from the glass surface. After that, a bending test and a light transmittance measurement of the adhesive based on JIS-K6856 were performed. The results are shown in Table 1.

Example 2 Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 50 parts by weight, bis (hydroxymethyl) tricyclo
[5.2.1.0 ^2,6 ] decane = β-carboxyl propionate methacrylate 2 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was mixed with 100 parts by weight of a mixture of 50 parts by weight. The mixture was stirred at 60 ° C until uniform. Thereafter, 10 parts by weight of γ- (acryloxypropyl) trimethoxysilane was mixed and stirred until uniform. The glass was adhered by the method described in Example 1. The bending test and light transmittance measurement of the adhesive based on JIS-K6856 were implemented. The results are shown in Table 1.

Example 3 Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 50 parts by weight, bis (hydroxymethyl) tricyclo
[5.2.1.0 ^2,6 ] decane = β-carboxyl propionate methacrylate 11 parts of pentaerythritol tetrakis (β-thiopropionate), photoinitiator to 100 parts by weight of a mixture of 50 parts by weight. As 2, 4, 6
2.2 parts by weight of trimethylbenzoyldiphenylphosphine oxide were mixed and stirred at 60 ° C. until uniform. 11 parts by weight of γ- (acryloxypropyl) trimethoxysilane were mixed and stirred until uniform.
Then, glass was adhered by the method described in Example 1. JI
The bending test and the light transmittance measurement of the adhesive based on S-K6856 were implemented. The results are shown in Table 1.

Example 4 Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 50 parts by weight, bis (hydroxymethyl) tricyclo
[5.2.1.0 ^2,6 ] decane = β-carboxyl propionate methacrylate 100 parts by weight of a mixture of 50 parts by weight, 2-hydroxyethyl acrylate 43
And 2.9 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photoinitiator were mixed and stirred at 60 ° C. until uniform. 14 parts by weight of γ- (acryloxypropyl) trimethoxysilane were mixed and stirred until uniform. Then, glass was adhered by the method described in Example 1. The bending test and light transmittance measurement of the adhesive based on JIS-K6856 were implemented. The results are shown in Table 1.

Example 5 Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 80 parts by weight, bis (hydroxymethyl) tricyclo
[5.2.1.0 ^2,6 ] decane = β-carboxyl propionate methacrylate ² parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photoinitiator based on 100 parts by weight of a mixture of 20 parts by weight. The parts were mixed and stirred at 60 ° C. until uniform. 10 parts by weight of γ- (acryloxypropyl) trimethoxysilane were mixed and stirred until uniform. Then, glass was adhered by the method described in Example 1. The bending test and light transmittance measurement of the adhesive based on JIS-K6856 were implemented. The results are shown in Table 1.

Example 6 Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane dimethacrylate 94 parts by weight, pentaerythritol tetrakis (β-thiopropionate) 6 parts, photoinitiated 2,4,6-as agent
0.05 parts by weight of trimethylbenzoyldiphenylphosphine oxide and 0.05 parts by weight of benzophenone were mixed and stirred at 60 ° C. until uniform. This was injected between two glass plates through a 0.4 mm spacer, and the output 40 above the glass surface at a distance of 40 cm.
Ultraviolet rays were irradiated for 5 minutes under a W / cm metal halide lamp. After removing the glass plate and washing with acetone,
It was cut into a length of 100 mm and a width of 25 mm. On this resin plate, a SiO ₂ film having a thickness of 200 Å was formed by a sputtering device (Tokuda Seisakusho; Model CFS-4ES). This S
The iO ₂ surface was wiped off with a gauze soaked with methanol and dried at room temperature until the odor disappeared.

Next, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 50
Parts by weight, bis (hydroxymethyl) tricyclo [5.
2.1.0 ^2,6 ] decane = β-carboxyl propionate methacrylate 2 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide are mixed with 100 parts by weight of a mixture of 50 parts by weight, and the mixture is heated to 60 ° C. Stir until uniform. The monomer mixture prepared by mixing 10 parts by weight of γ- (acryloxypropyl) trimethoxysilane and stirring until uniform was used as S of the plastic plate.
Drop a few drops on the surface of the iO ₂ sputter and bond it 12.5m
The above-mentioned two resin plates were bonded together by means of m with their SiO ₂ sputter surfaces facing each other. Then, UV irradiation was performed in the same manner as in Example 1. After that, a bending test and a light transmittance measurement of the adhesive based on JIS-K6856 were performed. The results are shown in Table 1.

Example 7 The surface of a glass plate having a thickness of 1.6 mm, a length of 100 mm and a width of 25 mm was wiped with a gauze moistened with methanol at room temperature until the odor disappeared. After drying, a few drops of the above-mentioned monomer mixed liquid were dropped and the mixture was rotated at 2000 rpm for 1 minute with a spin coater (1H-D7) manufactured by Mikasa Co., Ltd. Then, under a nitrogen atmosphere, ultraviolet rays were irradiated for 5 minutes under a metal halide lamp having an output of 40 W / cm at a distance of 40 cm. Then JIS-K5400-
A cross-cut peeling test and light transmittance measurement according to 8.5.1. The results are shown in Table 1.

[Comparative Example 1] Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 100 parts by weight based on 2,4,6-trimethylbenzoyldiphenylphosphine as a photoinitiator. Fin oxide 2
Parts by weight were mixed and stirred at 60 ° C. until uniform.
This is called a monomer mixture. In the same manner as in Example 1 below, two glass plates were laminated and UV-irradiated. Then J
The bending test and the light transmittance measurement of the adhesive based on IS-K6856 were implemented. The results are shown in Table 1.

[Comparative Example 2] 100 parts by weight of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate was used as a photoinitiator for 2,4,6-trimethylbenzoyldiphenylphosphine. Fin oxide 2
Parts by weight were mixed and stirred at 60 ° C. until uniform.
γ- (acryloxypropyl) trimethoxysilane 10
Parts by weight were mixed and stirred until uniform. This is called a monomer mixture. In the same manner as in Example 1 below, two glass plates were laminated and UV-irradiated. Then JIS-K68
Bending test and light transmittance measurement of the adhesive based on 56 were carried out. The results are shown in Table 1.

[Comparative Example 3] A film was formed on the glass from the monomer mixed solution described in Comparative Example 2 by the method described in Example 7, and then a peeling test and a light transmittance measurement were performed by the method described in Example 7. .

[0055]

[Table 1]

[0056]

EFFECT OF THE INVENTION The polymerizable composition of the present invention has a high light transmittance and is capable of well adhering optical materials such as glass,
It can adhere well. Therefore, it is not only useful as a bonding material or a coating material for glass plates and resin plates used for display bodies such as liquid crystal panels,
It is also used for adhesion of optical components for optical communication and waveguide materials.

[Brief description of drawings]

FIG. 1 is a drawing showing a configuration of a test piece in an adhesiveness test of an example of the present application.

FIG. 2 is a schematic diagram of an adhesiveness test of Examples of the present application.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Seiichiro Hayakawa             3-3-1 Chuo 8-chome, Ami Town, Inashiki District, Ibaraki Prefecture             Within Mitsubishi Chemical Corporation F-term (reference) 4J038 FA11 GA06 JA32 JA66 JC30                       KA03 KA09 PA17                 4J039 AD10 AD19 BE22 BE27 EA03                       EA06                 4J040 FA15 GA07 HB18 HB41 HD30                       KA38 PA32                 4J100 AL08Q AL66P BA15Q BA16Q                       BC12P BC12Q CA04 FA03                       JA01 JA03 JA07

Claims (13)

[Claims] 1. A polymerizable composition comprising the following components A and B. Component A: Bis (meth) aliphatic ring skeleton represented by the following formula (I)
Acrylate [Chemical 1] (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, m represents 1 or 2, n represents 0 or 1, and p and q each independently represent 0, 1 or 2.) Component B: an alicyclic skeleton mono (meta) represented by the following formula (II)
Acrylate [Chemical 2] (In the formula, R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a divalent hydrocarbon residue, m represents 1 or 2, n represents 0 or 1, and r and s are respectively It independently represents 0, 1 or 2.) 2. When the total amount of the component A and the component B is 100 parts by weight, the component A is 10 to 90 parts by weight and the component B is 10 parts by weight.
The polymerizable composition according to claim 1, wherein the polymerizable composition is about 90 parts by weight. 3. The polymerizable composition according to claim 1 or 2, wherein the polymerizable composition contains a radical polymerization initiator. 4. The polymerizable composition according to any one of claims 1 to 3, wherein the polymerizable composition contains a photopolymerization initiator. 5. The polymerizable composition according to claim 1, wherein the polymerizable composition contains a silane coupling agent. 6. Component A is bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate,
Bis (hydroxymethyl) tricyclo [5.2.1.0]
^2,6 ] decane = dimethacrylate and bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = acrylate methacrylate, wherein component B is bis (hydroxymethyl) tricyclo [5. 2.
1.0 ^2,6 ] decane = monoacrylate and bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane =
A reaction product of a compound selected from monomethacrylate and an intramolecular acid anhydride selected from succinic anhydride, maleic anhydride, glutaric anhydride, 3-methylglutaric anhydride, phthalic anhydride and trimellitic anhydride. The polymerizable composition according to any one of claims 1 to 5, wherein: 7. An adhesive containing the polymerizable composition according to any one of claims 1 to 6. 8. A coating agent containing the polymerizable composition according to any one of claims 1 to 6. 9. An ink containing the polymerizable composition according to any one of claims 1 to 6. 10. A coating composition containing the polymerizable composition according to claim 1. 11. A cured product obtained by polymerizing the polymerizable composition according to any one of claims 1 to 6. 12. An optical sheet comprising the cured product according to claim 11. 13. An optical plastic member comprising the cured product according to claim 11.