JPH09178907A - Light scattering body having adhesiveness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a light scattering body giving a flexible cured film by preparing a thermosetting adhesive compsn. based on a specified copolymer and dispersing particles different from the copolymer in refractive index in the compsn. SOLUTION: A thermosetting adhesive compsn. based on a copolymer of ethylene with an acrylate monomer and/or a methacrylate monomer and maleic acid and/or maleic anhydride is prepd. as a matrix and particles different from the copolymer in refractive index are dispersed in the compsn. The acrylate monomer and/or methacrylate monomer content of the copolymer is preferably 5-50wt.%. The compsn. preferably contains 0.1-10 pts.wt. org. peroxide and 0.01-5 pts.wt. silane coupling agent based on 100 pts.wt. of the copolymer. The particles are preferably fine particles different from the copolymer in refractive index by 0.01-0.2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a light-scattering body having thermosetting adhesiveness.

[0002]

2. Description of the Related Art Light diffusing materials that have been widely used hitherto have fine irregularities on the surface of glass or a transparent resin material, or uniformly disperse transparent fine particles having different refractive indexes in the glass or transparent resin material. The transmitted light is scattered by being dispersed. Further, a technique for imparting light scattering property by coating the surface of a transparent body with a cured film of a special silane compound mixture containing fine particles (Japanese Patent Laid-Open No. 58-58).
-42454) is also proposed.

[0003]

However, the above-mentioned scatterer having irregularities on the surface is liable to be soiled on the surface, and when a liquid such as water or oil is attached to the surface, the parallel light ray transmittance is increased and the haze is increased. The value decreases (the same phenomenon that the light scattering effect largely decreases when the frosted glass gets wet). Also,
As for the method, although the above-mentioned drawbacks are eliminated, since the material for dispersing the fine particles uses a transparent material having no hard self-adhesiveness such as glass, polycarbonate resin, polyester resin, acrylic resin or styrene resin, When using the body in combination with other members,
A temporary fixing process is required for the mounting, which complicates the process, and because it is a rigid body, the conformability of the shape to a member having some curved surface (such as a lamp cover) is poor,
There are problems that the use is extremely limited, a processing step is required, and the cost becomes high.

The present invention has been made in order to improve the above circumstances, and an object thereof is to provide a light-scattering body having a cured film having adhesiveness and being highly flexible.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a copolymer containing ethylene and an acrylate-based and / or methacrylate-based monomer and maleic acid and / or maleic anhydride is used. Using a thermosetting adhesive composition containing a polymer as a main component as a matrix,
By adding and dispersing particles having a refractive index different from that of the copolymer, the composition has adhesiveness, so that a light-scattering body having adhesiveness can be obtained. However, since it can be provided in liquid form, it can solve the above-mentioned conventional problems, and since the light-scattering body itself has adhesiveness, it does not require an adhesive for bonding with various members, and can be cured by curing. The cross-linked structure that is formed greatly improves durability after bonding, and the cured film is highly flexible, so it can be easily bonded to various curved surfaces as well as flat surfaces. That is, the present invention has been completed and the present invention has been completed.

That is, the present invention relates to (1) a thermosetting adhesive composition containing as a main component a copolymer of ethylene and an acrylate-based and / or methacrylate-based monomer and maleic acid and / or maleic anhydride. A light-scattering material having adhesiveness, characterized in that particles having a different refractive index from the copolymer are added and dispersed, (2) the thermosetting adhesive composition is ethylene and an acrylate-based and / or methacrylate-based monomer 0.1 to 10 parts by weight of an organic peroxide and 0.01 parts by weight of a silane coupling agent, based on 100 parts by weight of a copolymer consisting of and maleic acid and / or maleic anhydride.
The light-scattering body having adhesiveness according to (1), wherein the thermosetting adhesive composition comprises ethylene, an acrylate-based monomer, and / or a methacrylate-based monomer, and maleic acid. 0.1 to 50 parts by weight of at least one of an acryloxy group-containing compound, a methacryloxy group-containing compound and an allyl group-containing compound is added to 100 parts by weight of a copolymer consisting of an acid and / or maleic anhydride. (1) or the light scattering material having adhesiveness according to (2), (4) the particles to be added are composed of ethylene and an acrylate and / or methacrylate monomer, maleic acid and / or maleic anhydride The copolymer has a refractive index difference of 0.01 to 0.2 and an average particle diameter of 0.5 to 200 μm. And / or a methacrylate-based monomer and maleic acid and / or maleic anhydride 100 parts by weight, and 0.05 to 50 parts by weight is added (1), (2) or ( 3) A light-scattering body having the adhesiveness as described above.

The light-scattering body according to the present invention can be provided in the form of a sheet, can be attached to various members, and can be used as a scattering sheet by curing itself. Alternatively, it may be provided in a liquid form and applied on the surface of the transparent body and then cured. Further, since the light-scattering body itself has adhesiveness, an adhesive is not required for bonding to various members, and since it is a curable type, it has excellent durability including heat resistance.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. In the light-scattering body of the present invention, the matrix is a mixture of ethylene and an acrylate-based and / or methacrylate-based monomer with maleic acid and / or maleic anhydride. It is composed of a thermosetting adhesive composition containing a polymer as a main component.

The content of acrylate-based and / or methacrylate-based monomers in the copolymer of ethylene and acrylate-based and / or methacrylate-based monomers used in the present invention and maleic acid and / or maleic anhydride is 5 to 50% by weight. %, Particularly preferably 14 to 45% by weight. If this content is less than 5% by weight, the optical uniformity of the cured light-scattering body will not be sufficient, while
When the content is more than 10% by weight, the optical uniformity is good, but the strength and durability after curing may be significantly reduced.
The content of maleic acid and / or maleic anhydride is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight. If this content is less than 0.01%, the effect of improving the adhesive strength may be reduced, and if it exceeds 10%, the workability may be reduced.

Examples of the acrylate-based monomer and the methacrylate-based monomer include acrylic acid, methacrylic acid, and their esters.
Examples include lower alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate and ethyl (meth) acrylate, as well as glycidyl (meth) acrylate.
These may be used alone or in combination of two or more.

An organic peroxide can be added to the above composition from the viewpoint of imparting thermosetting property. As the organic peroxide, any one can be used as long as it decomposes at 70 ° C. or higher to generate radicals, but it is more preferable that the decomposition temperature with a half-life of 10 hours is 50 ° C. or higher. It can be selected and used in consideration of preparation conditions, curing (bonding) temperature, heat resistance of an adherend, storage stability and the like.

Examples of usable organic peroxides include 2,5-dimethylhexane-2,5-dihydroxyperoxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane- 3, di-t-butyl peroxide, t-butyl cumyl peroxide, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α-α′-bis (t-butylperoxyisopropyl) benzene, n-butyl-
4,4′-bis (t-butylperoxy) palerate,
1,1-bis (t-butylperoxy) butane, 1,1
-Bis (t-butylperoxy) cyclohexane, 1,
1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, t-butylperoxyacetate, methyl ethyl ketone peroxide, 2-5 dimethylhexyl-2,
5-bisperoxybenzoate, butyl hydroperoxide, p-methane hydroperoxide, p-
Chlorbenzoyl peroxide, tert-butylperoxyisobutyrate, hydroxyheptyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
Cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide, t-butyl peroxy (2-ethylhexanoate), m-toluoyl peroxide, benzoyl peroxide, t-
Butyl peroxyisobutyrate, 2,4-dichlorobenzoyl peroxide and the like can be mentioned.

As the organic peroxide, one of these is used.
The seeds may be used alone or in admixture of two or more, and the addition amount is 0.1 to 10 parts by weight based on 100 parts by weight of the above copolymer.

Further, a silane coupling agent can be added as an adhesion promoter to the adhesive composition of the present invention. As this silane coupling agent, vinyltriethoxysilane, vinyltris (β-methoxyethoxy)
Silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane , Vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane,
There are γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane and the like, and one of these may be used alone or two or more of them may be used in combination. The addition amount of these silane coupling agents is usually 0.1% with respect to 100 parts by weight of the copolymer.
01 to 5 parts by weight.

Further, an epoxy group-containing compound other than epoxysilane can be blended as an adhesion promoter. Such epoxy group-containing compounds include triglycidyl tris (2-hydroxyethylene) isocyanurate, neopentyl glycol diglycidyl ether,
1,6-hexanediol glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (E
O) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester,
Examples thereof include o-phthalic acid glycidyl ester, glycidyl methacrylate, and butyl glycidyl ether. A similar effect can be obtained by alloying a polymer containing an epoxy group. These epoxy group-containing compounds can be used alone or in combination of two or more, and the addition amount is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the above copolymer. .

Further, in order to improve or adjust the physical properties (mechanical strength, adhesiveness, optical properties, heat resistance, moist heat resistance, weather resistance, crosslinking rate) and the like of the light-scattering body having adhesiveness of the present invention, In the present invention, an acryloxy group, methacryloxy group or allyl group-containing compound can be added to the above composition.

Most commonly used compounds for this purpose are acrylic acid or methacrylic acid derivatives such as their esters and amides. In this case, the ester residues include methyl, ethyl, dodecyl, stearyl,
In addition to alkyl groups having 1 to 24 carbon atoms, particularly 1 to 18 such as lauryl, cycloalkyl groups such as cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-
Examples thereof include a halogenated substituent such as a hydroethyl group, a 3-hydroxypropyl group and a 3-chloro-2-hydroxypropyl group, a substituted alkyl group such as a hydroxyl group substituted and an amino group substituted. Also, acrylic acid or methacrylic acid and ethylene glycol, triethylene glycol, polyethylene glycol, glycerin, trimethylolpropane,
Esters with polyfunctional alcohols such as pentaerythritol are also used.

Diacetone acrylamide is a typical amide. Further, acryl or methacrylic acid ester such as trimethylolpropane, pentaerythritol and glycerin can be used as the polyfunctional crosslinking aid.

Examples of the allyl group-containing compound include triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, diallyl maleate, and the like. One kind or a mixture of two or more kinds thereof is 0.1 to 100 parts by weight of the above copolymer
It is used by adding 50 parts by weight, preferably 0.1 to 30 parts by weight. If it is less than 0.1 part by weight, the improving effect of improving the mechanical strength may be lowered, and if it exceeds 50 parts by weight, workability and film-forming property during preparation of the adhesive may be lowered.

Further, a hydrocarbon resin may be added to the composition of the present invention for the purpose of improving the workability of the light-scattering body and the workability such as bonding. In this case, the added hydrocarbon may be a natural resin type or a synthetic resin type. Rosin, rosin derivatives, and terpene resins are preferably used in the natural resin system. For rosin, gum-based resins, tall oil-based resins, and wood-based resins can be used. As the rosin derivative, rosin obtained by hydrogenation, heterogeneization, polymerization, esterification, and metal salification can be used.

As the terpene resin, a terpene phenol resin can be used in addition to the terpene resin such as α-pinene and β-pinene. Also, other natural resins such as dammar, cobal, and shellac may be used. On the other hand, in the case of synthetic resins, petroleum resins, phenol resins, and xylene resins are preferably used. As the petroleum resin, aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, hydrogenated petroleum resin, pure monomer petroleum resin, and cumarone indene resin can be used. As the phenolic resin, an alkylphenol resin and a modified phenol resin can be used. As the xylene-based resin, a xylene resin or a modified xylene resin can be used.

The addition amount of the above-mentioned hydrocarbon resin is appropriately selected, but is 1 to 200 relative to 100 parts by weight of a copolymer composed of ethylene and an acrylate-based and / or methacrylate-based monomer and maleic acid and / or maleic anhydride. Weight part is preferable, More preferably, it is 5-150 weight part.

The light source to which the light-scattering material having adhesiveness of the present invention is applied includes various light sources such as sunlight, fluorescent lamps and LEDs, among which, not only visible light but also harmful to the human body. Many light sources emit ultraviolet rays. Therefore, the light scatterer of the present invention may contain an ultraviolet absorber in the above composition for the purpose of blocking ultraviolet rays.

As the ultraviolet absorber, known ones can be used. As the benzophenone type ultraviolet absorber,
2,4-Digidroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,
2'-dihydroxy-4-methoxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like can be mentioned.

Further, as triazole type ultraviolet absorbers, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-) are used.
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-
t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ',
5'-di-t-aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t- Butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'. −
Examples thereof include hydroxybenzoate.

These UV absorbers may be used alone or in admixture of two or more, and the addition amount is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the above copolymer.

In addition to the above additives, the composition of the present invention comprises
Antiaging agents, dyes, processing aids and the like can be added within a range that does not impair the effects of the present invention.

On the other hand, the particles to be added and dispersed in the thermosetting adhesive composition (matrix) may be any particles having a refractive index different from that of the ethylene-vinyl acetate copolymer, In particular, a copolymer of the above ethylene, an acrylate-based monomer and / or a methacrylate-based monomer, maleic acid and / or maleic anhydride, and 0.01 to
0.2, particularly 0.05 to 0.2, and an average particle size of 0.5 to 200 μm, especially 1 to 200 μm.
Are preferable, and the addition amount thereof is 0.0 with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer.
5 to 50 parts by weight, particularly 0.1 to 45 parts by weight are preferred.

Examples of such fine particles include inorganic particles such as glass, quartz, silicon oxide, calcium carbonate, titanium oxide and zinc oxide, and organic particles such as silicone resin, acrylic resin, polyethylene, polystyrene and polyurethane.

To obtain the light-scattering body of the present invention, the constituent components of the composition and the particles are uniformly mixed and kneaded by an extruder, a roll or the like, and then this is extruded by a calender, roll, T-die, or inflation. It can be used by forming a film into a desired shape by a film forming method such as. At the time of film formation, embossing may be performed for the purpose of preventing blocking, facilitating pressure bonding with an adherend, and the like.

The sheet obtained as described above can be attached to a member by a conventional method. For example, lamination can be performed using a method such as a laminating method using a hot press, a direct laminating method using an extruder or a calender, or a thermocompression bonding method using a film laminator.

Further, each component can be uniformly dissolved in a solvent which does not affect the member, applied evenly on the surface of the member, temporarily press-bonded with another member, or can be heat-cured as it is. .

The curing conditions for the light-scattering material having adhesiveness of the present invention depend on the type of organic peroxide,
It is desirable that the temperature is 70 to 170 ° C., particularly 70 to 150 ° C. for 2 to 60 minutes, especially 5 to 30 minutes.

[0034]

Since the light-scattering body of the present invention has adhesiveness, it is necessary to separately use a pressure-sensitive adhesive or an adhesive when the conventional light-scattering body is formed by bonding various members together. The invention reduces the number of components called adhesive layers,
Further, since the light-scattering body itself has tackiness, there is no deviation due to slippage during alignment in the bonding process, and thus the labor can be greatly reduced. In addition, the light-scattering film formed has more flexibility than conventional ones, and thus can be combined with a complex shape other than a flat surface. Moreover, since it has a crosslinked structure by thermosetting, it is excellent in durability such as heat resistance and moisture heat resistance.

[0035]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1] Ethylene and acrylate and / or methacrylate monomers and maleic acid and / or
Or a copolymer consisting of maleic anhydride (Sumitomo Chemical Co.,
Bondane AX8390, ethylene content 68%, ethyl acrylate content 30%, maleic anhydride content)
1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane 2.0 per 100 parts by weight
Parts by weight, triallyl isocyanurate 2.0 parts by weight, γ
-0.5 parts by weight of glycidoxypropyltrimethoxysilane and 5 parts by weight of surface-treated calcium carbonate (Chemipron A manufactured by Chemipro Kasei Co., Ltd.) were added, and mixed with a mixing roll to obtain
After sufficiently kneading at a temperature of 0 ° C., a film having a thickness of 0.4 mm was formed by a calendar method. This sheet is installed on a halogen lamp and its front brightness (luminance meter, manufactured by Minolta: S-
When 100) was measured, it was 2300 cd / m ² .

Further, this sheet was sandwiched between a glass plate and a polyester film, placed in a rubber bag, and allowed to stand in an oven at 130 ° C. for 30 minutes while being deaerated by a vacuum pump to bond and integrate the glass plate and the polyester film. The obtained light scatterer was obtained. This light scatterer was placed on a halogen lamp and the front luminance was measured to be 2500
cd / m ² . Further, when the state of the light-scattering body was observed after the adhesive-composited light-scattering body was left in an oven at 100 ° C. for 500 hours, no change in appearance was observed and the front luminance was hardly changed. .

Example 2 The components used in Example 1 were uniformly dissolved in toluene, then uniformly coated on a polyester film with a roll coater and dried sufficiently.
A 30 μm light scattering coating was provided on the polyester film. The haze value and the total light transmittance of the light scatterer thus created were measured by a color computer (manufactured by Suga Test Instruments Co., Ltd .:
When measured by SM-5), the haze value is 52.7%,
The total light transmittance was 93.7%. Further, after the light-scattering body film was left in an oven at 130 ° C. for 30 minutes to cure the coating, the haze value and the total light transmittance were measured, and the haze value was 40.0%.
The total light transmittance was 95.3%.

Claims (4)

[Claims] 1. A thermosetting adhesive composition comprising, as a main component, a copolymer of ethylene and an acrylate-based monomer and / or a methacrylate-based monomer and maleic acid and / or maleic anhydride. A light-scattering body having adhesiveness, characterized in that particles different from each other are added and dispersed. 2. A copolymer 1 in which the thermosetting adhesive composition comprises ethylene and an acrylate-based and / or methacrylate-based monomer and maleic acid and / or maleic anhydride.
The adhesive light according to claim 1, wherein 0.1 to 10 parts by weight of an organic peroxide and 0.01 to 5 parts by weight of a silane coupling agent are added to 100 parts by weight. Scatterer. 3. A copolymer 1 in which the thermosetting adhesive composition comprises ethylene and an acrylate-based and / or methacrylate-based monomer and maleic acid and / or maleic anhydride.
3. The adhesive according to claim 1, wherein 0.1 to 50 parts by weight of at least one of an acryloxy group-containing compound, a methacryloxy group-containing compound and an allyl group-containing compound is added to 00 parts by weight. A light-scattering material. 4. A copolymer comprising ethylene, an acrylate-based monomer and / or a methacrylate-based monomer, maleic acid and / or maleic anhydride, and 0.01 are added particles.
Have a refractive index difference of 0.2 and an average particle size of 0.5 to
200 μm, and ethylene and acrylate and / or methacrylate monomers and maleic acid and / or
Alternatively, 0.05 to 50 parts by weight is added to 100 parts by weight of a copolymer of maleic anhydride, and the light having adhesiveness according to any one of claims 1, 2 and 3. Scatterer.