JP6835160B2 - Glass plate protection resin - Google Patents

Description

The present invention relates to a photocurable resin composition and a glass plate protective resin using the same.

Smartphones and tablets are becoming thinner for the purpose of increasing the screen size and weight. Along with this, the cover glass used is also becoming thinner. Therefore, highly strong chemically strengthened glass is widely used for the cover glass. In general, glass may have cracks on its end face due to contact or impact during the manufacturing process. In chemically strengthened glass, the strength may be significantly reduced due to this crack. It is also known that cracks cause cracks and reduce the yield. Therefore, a method has been developed in which a resin is applied to the end face to protect the glass from contact and impact and prevent the occurrence of cracks (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2012-11168 Special Table 2012-527399

Although methods have been developed to protect the glass by applying the resin to the glass, specific resin properties and compositions suitable for use in protecting the glass from contact and impact by applying the resin to the end face have been developed. Is not clear.
Therefore, in the present invention, these three are (1) firmly adhered to the glass, (2) have no tack from the viewpoint of work, and (3) have hardness for protecting the glass from impact. An object of the present invention is to provide a photocurable resin composition having characteristics and a glass plate protective resin using the photocurable resin composition.

In order to achieve the above object, the present inventors have found that the problem can be solved by the following.
That is, in the present invention, [1] (A) a monomer having an acrylic group, (B) an acrylic oligomer having a polymerizable unsaturated group having a weight average molecular weight of 800 to 10,000, and (C) a double bond in the molecule. The present invention relates to a photocurable resin composition containing a monomer which is a phosphoric acid compound having the above and (D) a photopolymerization initiator.
The present invention also relates to the photocurable resin composition according to the above [1], wherein the component [2] (B) contains a urethane oligomer.
Further, the present invention relates to a resin for protecting a glass plate using the photocurable resin composition according to [3] the above [1] or [2].

According to the present invention, a photocurable resin composition that adheres firmly to glass, has excellent workability because there is no tack, and has hardness for protecting the glass from impact, and the photocurable resin composition. It is possible to provide a resin for protecting a glass plate using an object.

It is the schematic of the method of applying the photocurable resin composition of this invention to a glass plate.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof.
The photocurable resin composition of the present embodiment contains (A) a monomer having an acrylic group. Since the acrylic resin has a high curing rate, it can be suitably used as a photocurable resin composition that requires short-time curing by containing a monomer having an acrylic group.
Examples of the (A) acrylic group-containing monomer used in the present embodiment include 2-hydrooxyethyl methacrylate, 2-hydrooxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate, methacrylic acid and Cardura E-10 ("Acrylate". Bifunctional methacrylic acid ester such as a reaction product of glycidyl ester of higher fatty acid manufactured by Shell Chemicals, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. Trifunctional methacrylic acid esters such as methacrylic acid ester and trimethylolpropane trimethacrylate, methyl acrylate, ethyl acrylate, lauryl acrylate, 2-hydrooxyethyl acrylate, 2-hydrooxypropyl acrylate, acrylic acid and Cadula E-10. Bifunctional acrylic acid esters such as monofunctional acrylic acid esters such as reactants, ethylene glycol diacrylates, diethylene glycol diacrylates, 1,6-hexanediol diacrylates, trimethylol propantriacrylates, pentaerythritol triacrylates, etc. Trifunctional acrylic acid esters, tetrafunctional acrylic acid esters such as pentaerythritol tetraacrylate, and hexafunctional acrylic acid esters such as pentaerythritol hexaacrylate are used, and two or more of these can be used in combination. ..

The photocurable resin composition of the present embodiment contains (B) an acrylic oligomer having a polymerizable unsaturated group having a weight average molecular weight of 800 to 10,000. Although it depends on the balance with the component (A), the weight average molecular weight of the acrylic oligomer is preferably 800 to 10000 from the viewpoint of curing speed, viscosity of resin and flexibility of coating film.
The weight average molecular weight in the present specification is a value measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene.
As the acrylic oligomer (B) having a polymerizable unsaturated group having a weight average molecular weight of 800 to 10,000 used in the present embodiment, for example, a urethane oligomer of a (meth) acrylate compound having a urethane bond can be exemplified. These can be used alone or in combination of two or more. It is preferable that the component (B) contains a urethane oligomer because the mechanical properties of the cured product can be easily controlled and the adhesion to the glass is good.
As the urethane oligomer, an addition reaction between a (meth) acrylic monomer having an OH group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Examples thereof include tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO or PO-modified urethane di (meth) acrylate, and carboxyl group-containing urethane (meth) acrylate. These can be used alone or in combination of two or more.

The photocurable resin composition of the present embodiment contains (C) a phosphoric acid compound having a double bond in the molecule. By having a double bond in the molecule, the component (C) can react with the acrylic group contained in the resin composition and polymerize. Further, since phosphoric acid has high polarity, it can be firmly adhered to the base material.
The monomer used in the present embodiment (C), which is a phosphoric acid compound having a double bond in the molecule, is an ethylenically unsaturated monomer having a phosphoric acid group or a phosphoric acid ester group, preferably a phosphoric acid group. Alternatively, it is a (meth) acrylate or allyl compound having a phosphate ester group, and specifically, mono (2-acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, or diphenyl (2-acryloyloxyethyl). Ethyl) phosphate, diphenyl (2-methacryloyloxyethyl) phosphate, phenyl (2-acryloyloxyethyl) phosphate, acid phosphooxyethyl methacrylate, metachloroyl oxyethyl acid phosphate monoethanolamine salt, 3-chloro-2-acid -Phonooxypropyl methacrylate, acid-phosphooxypolyoxyethylene glycol monomethacrylate, acid-phosphooxypolyoxypropylene glycol methacrylate, (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxy Examples thereof include -2-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, and allyl alcohol acid phosphate. Among them, acid phosphooxyethyl methacrylate, 2-methacryloyloxyethyl acid phosphate, and phosphorus-containing methacrylic acid ester {for example, CH ₂ = C (CH ₃ ) -COO (RO) _n- P (= O) (OH) ₂ } Is preferable. These can be used alone or in combination of two or more. The blending ratio of the component (C) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A) + component (B) from the viewpoint of stability and adhesion to glass, and is 0.1. A range of ~ 5 parts by mass is more preferable. When the blending ratio is 0.01 parts by mass or more, the adhesiveness to the glass is sufficient, and when it is 10 parts by mass or less, the stability of the obtained resin is good.

The photocurable resin composition of the present embodiment contains (D) a photopolymerization initiator.
The (D) photopolymerization initiator used in the present embodiment also includes what is called a sensitizer. Examples of such a photopolymerization initiator include aclysine, an acrydin-based compound having at least one acridinyl group in the molecule, and N, N- such as benzophenylone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2- Aromatic ketones such as morpholino-propanone-1, quinones such as alkylanthraquinone, benzoin ether compounds such as benzoylalkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethylketal, 2- (o-chlorophenyl) ) -4,5-Diphenylimidazole dimer, 2- (o-chlorophenyl) 4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) 4,5-diphenylimidazole dimer 2,4,5-Triaryl such as a compound, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. Examples thereof include imidazole dimer, N-phenylglycine, N-phenylglycine derivative, coumarin compound, onium salt and the like. These can be used alone or in combination of two or more.
The blending ratio of these (D) photopolymerization initiators is 0.1 to 20 parts by mass with respect to 100 parts by mass of the above-mentioned component (A) + component (B) from the viewpoint of curing speed, film forming property, and tackiness. The range of 1 to 15 parts by mass is preferable, and the range is more preferable. When the blending ratio is 0.1 parts by mass or more, photocuring is sufficient, and when it is 20 parts by mass or less, the characteristics (curability, adhesion, etc.) of the obtained cured product are good.

The glass plate protective resin of the present embodiment is obtained by blending the above components (A), (B), (C) and (D) and heating and dissolving them.

Further, a coupling agent, a polymerization inhibitor, a colorant and the like can be added to the glass plate protective resin according to the present embodiment, if necessary.

Coupling agents include titanate-based coupling agents and silane-based coupling agents, and titanate-based coupling agents include titanate-based coupling agents having at least an alkylate group having 1 to 60 carbon atoms and alkylphosphite groups. Examples thereof include a titanate-based coupling agent having an alkyl phosphate group, a titanate-based coupling agent having an alkyl phosphate group, and a titanate-based coupling agent having an alkyl pyrophosphate group. Specifically, isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyl dialacrylic titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraoctylbis (ditridecylphosphite) titanate. , Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like.

The silane-based coupling agents include amino-based silane coupling agents, ureido-based silane coupling agents, vinyl-based silane coupling agents, methacrylic-based silane coupling agents, epoxy-based silane coupling agents, and mercapto-based silane coupling agents. Examples thereof include agents and isocyanate-based silane coupling agents. Specifically, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, ureidopropyltri. Ethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) Examples thereof include ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanoxidetrimethoxysilane, and these can be used alone or in combination of two or more.

Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol, quinones such as pyrogallol, and other commonly used agents. Used.
Examples of the defoaming agent include those generally used such as silicone-based oil, fluorine-based oil, and polycarboxylic acid-based polymer.
The glass plate protective resin of the present embodiment is applied to the end face of the cover glass for electronic parts and the periphery thereof by a dispenser device or the like, and is a lamp type or LED type UV irradiation device using a high-pressure mercury lamp, a metal halide lamp or the like as a light source. Is used by irradiating a required amount of ultraviolet rays to cure the glass.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]
37.8 parts by mass of isobornyl acrylate as component (A-1), 4.2 parts by mass of acryloylmorpholin as component (A-2), UN-904 (manufactured by Negami Kogyo Co., Ltd.) as component (B-1) Name "Art Resin UN-904", Urethane Acrylate oligomer, Weight Average Molecular Weight: 4900) 29 parts by mass, UN-6060S (manufactured by Negami Kogyo Co., Ltd., Trade Name "Art Resin UN-6060S") as a component (B-2), Urethane acrylate oligomer, weight average molecular weight: 6000) 29 parts by mass, (C) component (C) 0.5 parts by mass of ethylene oxide-modified dimethacrylate, and (D) component (1-hydroxycyclohexyl) 10 parts by mass of phenylmethanone. A photocurable resin composition was obtained by heating and stirring at 60 ° C.

[Example 2]
The photocurable resin composition was prepared in the same manner as in Example 1 except that the component (B-1) was changed to DPHA-40H (manufactured by Nippon Kayaku Co., Ltd., trade name, polyfunctional oligomer, weight average molecular weight: 2000). Obtained.

[Comparative Example 1]
A photocurable resin composition was obtained in the same manner as in Example 1 except that 0.5 parts by mass of ethylene oxide-modified dimethacrylate phosphate of Example 1 was not added.

[Comparative Example 2]
Photocuring in the same manner as in Example 1 except that 0.5 part by mass of ethylene oxide-modified dimethacrylate of ethylene oxide of Example 1 was changed to 0.5 part by mass of 3-isocyanatepropyl-triethoxysilane of a silane coupling agent. A sex resin composition was obtained.

[Comparative Example 3]
35 parts by mass of 2-hydrooxyethyl acrylate and 10 parts by mass of lauryl acrylate as component (A), TE-2000 (manufactured by Nippon Soda Co., Ltd., trade name, acrylic-modified polybutadiene resin, weight average molecular weight: about 9000) as component (B) ) 52 parts by mass, 0.2 parts by mass of N, N'-tetraethyl-4,4'-diaminobenzophenone instead of component (C) to impart adhesion between resin and glass, 2-as component (D) 2.5 parts by mass of (o-chlorophenyl) -4,5-diphenylimidazole dimer was heated and stirred at 60 ° C. to obtain a photocurable resin composition.

[Glass adhesiveness]
Soda glass (float glass) was wiped well with Bencot (manufactured by Asahi Kasei Fibers Co., Ltd., product name (“Bencot” is a registered trademark)) soaked with acetone to form test substrate 1 (Fig. 1 (a)). .. As shown in FIG. 1 (b), a tape having a thickness of 25 μm was attached in parallel on the glass surface with a width of 4 cm to form a guide 2. As shown in FIG. 1 (c), the resin 3 was hung on the surface on which the guide 2 was formed and stretched with a glass rod 4 to prepare a resin film 5 having a uniform thickness as shown in FIG. 1 (d). ..
The resin film produced above was cured with a UV irradiation device manufactured by Eye Graphics Co., Ltd. The irradiation output is measured with an irradiance meter (manufactured by Ushio Denki Co., Ltd.), and irradiation is performed so that the total irradiation amount is 1000 mJ / cm ^{2 with an irradiation intensity of 150 mW / cm 2} to obtain the desired [glass plate A with resin]. It was.
A cross cut was made in the coating film according to the method of JIS K-5600 to prepare a grid of 100 squares.
The glass plate with resin was put into a PCT (pressure cooker tester) and heated at 121 ° C. for 30 minutes. The water content of the test piece taken out from the PCT was wiped off, and the test piece was placed in a constant temperature bath at 80 ° C. for 10 minutes to prepare a test piece for adhesiveness evaluation.
The test piece subjected to the above treatment was subjected to a peeling test with a tape according to the method of JIS K-5600-5-6. The glass adhesiveness evaluation was shown by the number of remaining glass in 100 squares.

[Tackiness]
The tackiness was evaluated by touching the [glass plate A with resin] prepared by glass adhesiveness with a finger. Those with stickiness were evaluated with "x", and those without stickiness were evaluated with "○".

[hardness]
The hardness was evaluated by a pencil hardness test. The test was carried out according to JIS K-5600-5-4 by the mechanical method. In the present invention, the pencil hardness at which the protective effect of glass is recognized is set to HB or higher.

Table 1 shows the evaluation results of glass adhesiveness, tackiness, hardness, and curing time (the time until the liquid resin solidifies by curing and loses fluidity is defined as the curing time).

As shown in Table 1, it can be seen that there is no resin satisfying all the characteristics required for the glass plate protective resin in the comparative example as compared with the examples.

Although the specific embodiments have been described above, various modifications and substitutions can be made without departing from the spirit and scope of the present invention. Therefore, the present invention has been illustrated by way of example and is not limited thereto.

1 ... test substrate, 2 ... guide, 3 ... resin, 4 ... glass rod, 5 ... resin film.

Claims (5)

A resin for protecting a glass plate using a photocurable resin composition.
The photocurable resin composition has (A) a monomer having an acrylic group, (B) an acrylic oligomer having a polymerizable unsaturated group having a weight average molecular weight of 800 to 10,000, and (C) a double bond in the molecule. It contains a monomer which is a phosphoric acid compound having (D) and (D) a photopolymerization initiator.
The component (A) contains at least one selected from the group consisting of a monofunctional acrylic acid ester and a monofunctional methacrylic acid ester.
The component (B) is seen containing a urethane oligomers,
The blending ratio of the component (C) is 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
A resin for protecting a glass plate , wherein the compounding ratio of the component (D) is 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). The glass plate protective resin according to claim 1, wherein the component (A) contains isobornyl acrylate. The glass plate protective resin according to claim 1 or 2, wherein the component (C) contains ethylene oxide-modified dimethacrylate phosphate. Any one of claims 1 to 3, wherein the blending ratio of the component (C) is 0.01 to 0.5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). The resin for protecting the glass plate described in the section. The item according to any one of claims 1 to 4, wherein the blending ratio of the component (D) is 10 to 20 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). Resin for protecting glass plates.