JPWO2014115886A1 - Method for manufacturing thin glass substrate - Google Patents

Abstract

A composition comprising a resin obtained by reacting a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol with a crosslinking agent (a2) as a component (A). A method for producing a glass substrate thinned by etching, comprising: a step of applying to an outer peripheral portion to form an outer peripheral seal; and a step of thinning by etching.

Description

  The present invention relates to a method for manufacturing a thinned glass substrate including a step of forming a peripheral seal of a glass substrate using a resin composition.

  In recent years, with the demand for thinning of display panels such as liquid crystal televisions and mobile phones, thinning of display devices such as liquid crystal display panels is also required. For thinning the display device, a method of manufacturing a display device by bonding thin glass and a method of physically or chemically thinning a glass portion after manufacturing the display device are being studied. Such a laminated glass is also called a glass panel. Among these, in the method of manufacturing a display device by bonding thin glass, it is considered that the possibility of the glass panel being damaged during the manufacturing process is increased due to insufficient strength due to the use of the thin glass. For this reason, the method of grinding the glass surface after bonding the glass of the thickness used normally and manufacturing a glass panel, and reducing the thickness of glass is proposed (patent documents 1-3).

  The above glass surface grinding methods include a physical grinding method such as polishing and a chemical grinding method (etching) using hydrofluoric acid (HF), etc., but it is easy to control the thickness of a glass having sufficient strength. Etching using hydrofluoric acid or the like is widely used because it is possible to perform batch processing.

  However, in etching using hydrofluoric acid or the like, when the glass panel is immersed in an etching solution, the etching solution may enter the inside of the glass panel and cause various problems. Then, the sealing agent (sealing agent) which prevents such penetration | invasion of etching liquid is proposed (patent document 4).

  A method using a photosensitive resin composition containing an alkali-soluble resin having a lactam group or an imide group and an acrylate monomer having a lactone structure has also been proposed (Patent Document 5).

Japanese Patent No. 2722798 JP 2004-77640 A JP 2004-317981 A JP 2007-314660 A JP 2010-106048 A

  Patent Document 4 contains an oligomer obtained by reacting an epoxy resin having an epoxy equivalent of 400 to 2500 eq / g with an ethylenically unsaturated group-containing monocarboxylic acid, an ethylenically unsaturated group-containing compound and a photopolymerization initiator. And the sealing agent used in order to prevent the penetration | invasion of etching liquid in the case of the etching of a glass substrate is proposed. Here, in order to ensure the barrier property against etching using hydrofluoric acid, it is necessary to use a high-viscosity resin composition having a large molecular weight as a sealing agent.

  However, due to the demand for thinner display devices, longer etching time and higher accuracy of etching amount are required. When a sealing agent is applied to a glass panel having a narrow gap, a conventional sealing agent is required. In addition to requiring a long time for the sealing agent to permeate the gaps in the glass panel, the viscosity of the sealing agent is poorly penetrating into the gaps of the sealing agent, and the sealing agent that could not fully penetrate inside Sometimes it swelled outside the glass panel, creating a convex bulge. For this reason, after the etching, the convex bulge becomes thicker than the glass panel, and the glass panel may be damaged. Therefore, a sealant having a low viscosity and excellent permeability to the gap has been demanded. However, a sealant having a low viscosity has a drawback that the molecular weight is low and the hydrofluoric acid barrier property is lowered. Further, according to the study of the present inventors, the method of Patent Document 5 still cannot be said to have sufficient hydrofluoric acid barrier properties.

  The present invention has been made in view of the above problems, and includes a step of forming a seal on the outer periphery of glass using a resin composition having both excellent hydrofluoric acid barrier properties and excellent permeability. An object of the present invention is to provide a method for producing a thinned glass substrate.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by using a polyester resin and / or a polyurethane resin produced from polybutadiene polyol as a raw material, and the present invention has been completed.

That is, this invention relates to the following 1-13.
1. A composition comprising a resin obtained by reacting a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol with a crosslinking agent (a2) as a component (A). A method for producing a glass substrate thinned by etching, comprising: a step of applying to an outer peripheral portion to form an outer peripheral seal; and a step of thinning by etching.
2. 2. The method for producing a substrate according to 1, wherein the reaction between the polyol (a1) and the crosslinking agent (a2) is an ester bond forming reaction.
3. 2. The method for producing a substrate according to 1, wherein the reaction between the polyol (a1) and the crosslinking agent (a2) is a urethane bond forming reaction.
4). The said polyol (a1) is hydrogenated polybutadiene polyol, The manufacturing method of the board | substrate in any one of 1-3 characterized by the above-mentioned.
5. The method for producing a substrate according to any one of 1 to 4, wherein the resin of the component (A) further comprises a (meth) acrylate group.
6). The method for producing a substrate according to any one of 1 to 5, wherein the resin of the component (A) further has an alkali-soluble group.
7). The said composition contains the (B) ethylenically unsaturated monomer further, The manufacturing method of the board | substrate in any one of 1-6 characterized by the above-mentioned.
8). 8. The method for producing a substrate according to 7, wherein the ethylenically unsaturated monomer is an aliphatic or alicyclic alkyl (meth) acrylate having 6 or more carbon atoms.
9. The method for producing a substrate according to any one of 1 to 8, wherein the composition further comprises (C) a photopolymerization initiator.
10. 10. The method for manufacturing a substrate according to any one of 1 to 9, wherein the etching is wet etching.
A substrate manufactured by the manufacturing method according to any one of 11.1 to 10.
12. An electronic component using the substrate according to 12.11.
13. The component (A) includes a resin obtained by reacting a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol with a crosslinking agent (a2). Resin composition for glass processing.

  The polybutadiene polyol (a1) and the crosslinking agent (a2) form an ester bond or a urethane bond, and if necessary, a resin containing a (meth) acrylate group and / or an alkali-soluble group is an excellent hydrofluoric acid. Shows barrier properties, and does not corrode even with high concentrations of acid or alkali. Furthermore, (B) it is possible to adjust the viscosity to be lower than that of a conventional resin composition by containing an ethylenically unsaturated monomer, and the effect that the hydrofluoric acid barrier property does not decrease when cured. Play. For this reason, it is possible to produce a peripheral seal that has excellent penetrability and produces few convex bulges when applied to the outer periphery of the glass panel, reducing the possibility of damage when the glass panel is thinned. can do.

  Further, since it has excellent curability, it can be cured well even by a photo radical initiator cleaved with light having a relatively weak energy of λ = 405 nm. Therefore, the curing process by ultraviolet light with λ <400 nm that damages the liquid crystal layer can be avoided, and the ultraviolet cut film for protecting the liquid crystal layer, which is necessary in the conventional sealing material curing process, can be reduced.

  The resin composition of the present application may further contain a silane coupling agent as necessary. However, this resin has been conventionally used as an adhesive, and a silane coupling agent that causes residue is added. Demonstrate good adhesion. Therefore, the content of the silane coupling agent, which was essential in the conventional resin composition for sealing materials, can be reduced, and when a defect occurs in the outer peripheral seal, it is easy to peel and re-apply. Have.

  From the above, the present resin is very promising as an acid / alkali prevention film excellent in workability, and the etching process of a glass panel using the present resin as an outer peripheral seal can improve the work efficiency as compared with the conventional one.

The thin glass substrate manufactured using the manufacturing method of this invention is shown.

  Hereinafter, the resin composition described in the present application and a method for producing a thinned glass panel formed using the composition of the present invention will be described in detail. The manufacturing method of the glass substrate thinned by etching according to the present invention includes a step of applying the resin composition of the present invention to the outer peripheral portion of the glass panel to form an outer peripheral seal, and a step of thinning by etching. It is characterized by including.

  Examples of a method for applying the resin composition to the outer peripheral portion of the glass panel include manual and application devices such as a dispenser.

  The substrate according to the present invention is manufactured by the above manufacturing method, and the electronic component according to the present invention is characterized by using the substrate.

<Resin composition>
In the resin composition of the present invention, the polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol as the component (A) and the crosslinking agent (a2) are ester bonds or urethane bonds. And optionally containing a (meth) acrylate group and / or an alkali-soluble group, and optionally (B) having at least one ethylenically unsaturated double bond It contains a compound and / or a radiation radical polymerization initiator (C).

<(A) Polybutadiene resin>
The polybutadiene resin (hereinafter also referred to as resin (A)) used as the component (A) in the present invention is a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol. And a crosslinking agent (a2), more specifically, the crosslinking agent (a2) is a polyvalent carboxylic acid (a2-1) and / or a polyvalent acid chloride (a2-2), and a polyol (a1 ) And an ester bond, and a polybutadiene polyurethane resin in which the crosslinking agent (a2) is a polyisocyanate (a2-3) and a urethane bond is formed with a polyol (a1). Say. If necessary, a part of the polyol (a1) is a monool or polyol containing an alkali-soluble group such as (meth) acrylate (b) and / or a carboxyl group containing a substituent selected from halogen, an isocyanate group and a hydroxyl group. Instead of (c), it may be reacted with a crosslinking agent (a2).

  Each component which comprises this resin (A) is demonstrated below.

<Polyol (a1)>
Examples of the polyol (a1) selected from the polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol used in the present invention include those obtained by hydrogenating unsaturated bonds in the molecule, polyethylene-based polyols, Polypropylene polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols and the like can be mentioned. As the polybutadiene polyol, those having a 1,4-bond type, a 1,2-bond type or a polybutadiene structure in which they are mixed and two hydroxyl groups in the molecule are preferable, and hydroxyl groups are respectively formed at both ends of the chain polybutadiene structure. What has is more preferable. These polyols can be used singly or in combination of two or more.

  Examples of the polybutadiene polyol include conventionally known general ones, such as liquid polybutadiene having hydroxyl groups at both ends, such as NISSO PB (G series) of Nippon Soda Co., Ltd., Poly-Pd of Idemitsu Petrochemical Co., Ltd. ; Nipponso Soda Co., Ltd. NISSO PB (GI series), Mitsubishi Chemical Co., Ltd. polytail H, polytail HA, etc. Hydrogenated polybutadiene having hydroxyl groups at both ends; at both ends such as Poly-iP made by Idemitsu Petrochemical Co., Ltd. Liquid C5 polymer having a hydroxyl group, such as Epaul manufactured by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene having hydroxyl groups at both ends, such as TH-1, TH-2, TH-3 manufactured by Kuraray Co., Ltd. Although what is marketed can be used, it is not limited to this.

  Among the polyols, hydrogenated polybutadiene polyol is particularly preferably used in terms of barrier properties against hydrofluoric acid and film strength.

The weight average molecular weight of such a polyol is not particularly limited, but the lower limit is preferably 300 or more, more preferably 500 or more, and still more preferably from the viewpoint of improving the acid resistance of the resulting resin thin film. 1000 or more. On the other hand, the upper limit is preferably 30000 or less, more preferably 15000 or less, even more preferably 6000 or less, and still more preferably 3000 or less, from the viewpoint of suppressing an excessive increase in the viscosity of the resin composition and maintaining workability. It is.
The iodine value is 0 to 50, preferably 0 to 20, and the hydroxyl value is 15 to 400 mgKOH / g, preferably 30 to 250 mgKOH / g.

<Polyvalent carboxylic acid (a2-1)>
The polyvalent carboxylic acid (a2-1) used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polycarboxylic acids such as phthalic acid. 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Aromatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid and the like; hexahydro Phthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohe Suntory carboxylic acid, cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane alicyclic polycarboxylic acids such as tetracarboxylic acid; and the like.

  Among the polyvalent carboxylic acids, aromatic or alicyclic polyvalent carboxylic acids are particularly preferably used in terms of barrier properties to hydrofluoric acid and film strength.

  These polyvalent carboxylic acids can be used singly or in combination of two or more.

<Polyacid chloride (a2-2)>
The polyvalent acid chloride (a2-2) used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyvalent acid chlorides, such as phthalic dichloride, 3,4-dimethylphthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, pyromellitic acid dichloride, trimellitic acid dichloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride, 3,3 ', 4,4 '-Benzophenone tetracarboxylic acid tetrachloride, aromatic polyvalent acid chlorides; succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, 1,2,3,4-butanetetracarboxylic acid tetrachloride, maleic acid dichloride, fumarate Aliphatic polyvalent acid chlorides such as acid dichloride and itaconic acid dichloride; hexahydrophthal And the like; acid dichloride, hexahydroterephthalic acid dichloride, cyclopentane tetracarboxylic acid, alicyclic polyvalent acid chloride and the like.

  Among the polyvalent acid chlorides, aromatic or alicyclic polyvalent acid chlorides are particularly preferably used in terms of barrier properties to hydrofluoric acid and film strength.

  These polyvalent acid chlorides can be used singly or in combination of two or more.

<Polyisocyanate (a2-3)>
The polyisocyanate (a2-3) used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic and alicyclic polyisocyanates, among which tolylene diisocyanate and diphenylmethane diisocyanate ( Also called methylene diphenyl diisocyanate), hydrogenated diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate (isophorone diisocyanate) Also called diborns such as norbornene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane. Aneto or their trimers, biuret type polyisocyanate is preferably used.

  The molecular weight of the polyisocyanate (a2-3) is preferably 150 to 700 from the viewpoint of reactivity with a hydroxyl group.

  These polyisocyanates can be used singly or in combination of two or more.

  The resin (A) of the present invention is characterized in that the polybutadiene polyol (a1) and the crosslinking agent (a2) form an ester bond or a urethane bond. These can be selected according to the purpose, but urethane bonds are more preferable from the viewpoint of film strength and substrate adhesion. The reason is that the urethane bond has a stronger hydrogen bond than the ester bond, and thus has excellent affinity between molecules and the substrate.

<Manufacture of resin (A)>
Resin (A) is obtained by reacting polyol (a1) with polyvalent carboxylic acid (a2-1), polyvalent acid chloride (a2-2) or polyisocyanate (a2-3). When it is desired to form an ester bond, it may be reacted with a polyvalent carboxylic acid (a2-1) or a polyvalent acid chloride (a2-2). When a urethane bond is desired to be formed, polyisocyanate (a2-3) is added. What is necessary is just to make it react.

  The reaction is preferably carried out in a solvent. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogen-based carbonization such as carbon tetrachloride, chloroform and 1,2-dichloroethane. Hydrogens; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; nitriles such as acetonitrile, propionitrile; ethyl acetate, propionic acid Carboxylic acid esters such as ethyl; nitrogen-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone Dimethyl sulfoxide, sulfur Sulfur-containing aprotic polar solvents such as Horan like. These solvents may be used alone, or two or more of these may be mixed and used. Preferably, toluene, cyclohexanone, etc. are mentioned.

  Although the usage-amount (reaction concentration) of a solvent is not specifically limited, You may use a 0.1-100 mass times solvent with respect to a polyol (a1). Preferably it is 1-10 mass times, More preferably, it is 2-5 mass times.

  Although reaction temperature is not specifically limited, When reaction forms a urethane bond, the range of 30-90 degreeC, especially 40-80 degreeC is preferable.

  When the reaction forms an ester bond, a range of 30 to 150 ° C, particularly 80 to 150 ° C is preferable.

  The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

  In such a reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such a catalyst include organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, and octoic acid. Metal salts such as zinc, tin octoate, cobalt naphthenate, stannous chloride, stannic chloride, pyridine, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N -Amine-based catalysts such as ethylmorpholine.

  Among these, when a urethane bond is formed, dibutyltin dilaurate (hereinafter also referred to as dibutyltin dilaurate) is preferable.

  In the case of forming an ester bond, pyridine and 1,8-diazabicyclo [5.4.0] -7-undecene are preferable.

  Further, a (meth) acrylate group may be introduced into the resin (A) of the present invention for the purpose of imparting curability by radiation. The method for introducing the (meth) acrylate group is not particularly limited, and is selected from halides such as 2-chloroethyl acrylate, isocyanate compounds such as 2-isocyanatoethyl acrylate, and hydroxyl-containing compounds such as hydroxyethyl acrylate (meta ) The acrylate (b) is mixed with the polyol (a1) and the polyvalent carboxylic acid (a2-1), the polyvalent acid chloride (a2-2) or the polyisocyanate (a2-3) at the time of reaction. (A) can be introduced.

  Any one of these (meth) acrylate compounds can be selected and / or mixed depending on the purpose, but a hydroxyl group-containing (meth) acrylate compound is more preferable because of easy availability of raw materials.

  The halogen group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-chloroethyl (meth) acrylate, 2-chloropropyl (meth) acrylate, 2-chlorobutyl (meth) acrylate, and 2-chloroethylacryloyl phosphate. 4-chlorobutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-chloropropyl phthalate, 2-chloro-3-acryloyloxypropyl (meth) acrylate, and the like.

  The isocyanate group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-isocyanate ethyl (meth) acrylate, 2-isocyanate propyl (meth) acrylate, 2-isocyanate butyl (meth) acrylate, and 2-isocyanate ethyl. Examples include acryloyl phosphate and 4-isocyanatobutyl (meth) acrylate.

  The hydroxyl group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxyethylacryloyl. Phosphate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, caprolactone Modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate Over doors and the like.

  Among these, a hydroxyl group-containing (meth) acrylate having an alkyl group having 2 to 20 carbon atoms is useful in terms of tackiness and weather resistance.

  In addition, an alkali-soluble group may be introduced into the resin (A) for the purpose of imparting developability and / or peelability with an aqueous alkali solution. Examples of the method for introducing an alkali-soluble group into the resin (A) include a method of mixing with an alkali-soluble resin to form a composition, or a method of introducing an alkali-soluble group into the resin by chemical bonding. From the viewpoint of solubility in the resin, a method of introducing an alkali-soluble group into the resin by chemical bonding is more preferable.

  Examples of the alkali-soluble group include an acidic group such as a carboxyl group or an acid-dissociable group such as a t-butyl ester group of a carboxylic acid, and any one selected and / or mixed depending on the purpose is used. Can do.

  From the viewpoint of production of the resin (A) of the present invention, it is preferable to use a monool or polyol (c) containing an alkali-soluble group such as a carboxyl group as the alkali-soluble group from the viewpoint of easy availability of raw materials.

  For example, a monool or polyol (c) containing an alkali-soluble group, a polyol (a1), a polyvalent carboxylic acid (a2-1), a polyvalent acid chloride (a2-2) or a polyisocyanate (a2-3) By mixing in the reaction, an alkali-soluble group can be introduced into the resin (A).

  The carboxyl group-containing monool or polyol (c) is not particularly limited, and examples of the carboxyl group-containing monool include hydroxyacetic acid, hydroxypropionic acid, hydroxybutanoic acid, 12-hydroxystearic acid, hydroxypivalic acid, 15 -Hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, malic acid, citric acid and the like. Examples of the carboxyl group-containing polyol include 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3 , 5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4 -Hydroxyph Yl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, and homogentisic acid.

  Among the carboxyl group-containing monool or polyol (c), 12-hydroxystearic acid and 2,2-bis (hydroxyethyl) propionic acid are particularly preferable in terms of adhesive strength.

  In addition, as a specific example of the carboxyl group-containing monool or polyol (c) in the specification, it is expressed by a general common name “... acid”, but each of these specific examples has one COOH group. A compound having at least one and having at least one OH group.

  When a (meth) acrylate group and / or an alkali-soluble group is introduced into the resin (A) of the present invention, (i) a polyisocyanate (a2-3) contains a polyol (a1) and, if necessary, a carboxyl group Monool or polyol (c) and, if necessary, (meth) acrylate (b) are charged and reacted together, (b) polyisocyanate (a2-3) and polyol (a1), and optionally carboxyl group A method of reacting (meth) acrylate (b) if necessary after reacting the contained monool or polyol (c), (c) polyisocyanate (a2-3), and (meth) acrylate if necessary After reacting (b), a method of reacting a carboxyl group-containing monol or polyol (c) as necessary is mentioned.

  When a (meth) acrylate group and an alkali-soluble group are introduced into the resin (A) of the present invention, for example, a polyol (a1) and a polyisocyanate (a2-3) are converted into k: k + 1 (molar ratio) (k is 1 or more). The reaction is carried out at a reaction molar ratio of 1) to obtain an isocyanate group-containing compound [a], and then the carboxyl group-containing monool or polyol (c) is reacted with the isocyanate group-containing compound [a] in a 1: 1 reaction. The reaction is carried out at a molar ratio, and the resulting reaction product is reacted with (meth) acrylate (b) at a reaction molar ratio of 1: 1 to 1.10, or the isocyanate group-containing compound [a] is ( The (meth) acrylate (b) is reacted at a reaction molar ratio of 1: 1, and the reaction product obtained is further reacted with a carboxyl group-containing monool or polyol (c) of 1: 1 to 1.10. A method of reacting a ratio is preferred.

  Further, in the production of the resin (A), when the resulting resin (A) has a high viscosity, an ethylenically unsaturated monomer (B) described later is charged in a reaction can in advance as necessary, The resin (A) can also be produced by reacting each component in the unsaturated monomer (B). For the same purpose, the resin (A) can also be produced in a solvent described later, but it is necessary to remove the solvent from the resin (A) after completion of the reaction. Because the gap (gap) between the glass panels is very narrow as 2 to 20 μm, if the solvent is contained in the resin composition, even if heated, the solvent remains without volatilization, and the hydrofluoric acid barrier property This is because a decrease occurs.

  Thus, the resin (A) used in the present invention is obtained. In the present invention, the weight average molecular weight of the resin (A) is preferably 5,000 to 400,000, and more preferably 10,000 to 200,000. Preferably there is. When the weight average molecular weight is less than 5,000, the strength of the coating film is insufficient, and when it exceeds 200,000, the solubility and the coating property are deteriorated.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (high-performance liquid chromatography (the Showa Denko company make, "Shodex GPC system-11 type | mold")). Exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / book, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) 3 Measured by using this series.

  The glass transition temperature of the resin (A) [measured by TMA (thermomechanical analysis) method] is not particularly limited and can be selected according to the method of use. That is, when the glass transition temperature is 0 ° C. or higher, the outer peripheral seal surface is not tacky and is preferable from the viewpoint of workability. If the glass transition temperature is 0 ° C or lower, the adhesion is even better, but the outer surface seal surface is tacky, but the seal that has risen outside the glass panel is peeled off by a physical method such as tearing. By doing so, it is possible to leave only the seal that has permeated the glass panel, and it is possible not to deteriorate the workability.

  Furthermore, in this invention, it is preferable that the number of ethylenically unsaturated groups in 1 molecule of resin (A) is 1-3, and when it exceeds 3, the adhesiveness of the cured film by active energy ray irradiation will fall. Moreover, the hydrofluoric acid barrier property is also lowered, which is not preferable.

  It is also possible to use a commercially available resin (A) produced in this manner. Examples of commercially available products include UC-203 manufactured by Kuraray Co., Ltd. and UV-manufactured by Nippon Synthetic Chemical Co., Ltd. 3610ID80, UV-3630ID80, etc. are mentioned.

<(B) Ethylenically unsaturated monomer>
In the present invention, an ethylenically unsaturated monomer (B), that is, a compound having at least one ethylenically unsaturated double bond can be further contained for the purpose of improving adhesive properties and coatability. . The ethylenically unsaturated monomer (B) is not particularly limited, and examples thereof include monofunctional (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher (meth) acrylates. From the standpoint, monofunctional (meth) acrylate is effective, and (meth) acrylate of aliphatic or alicyclic alkyl having 6 or more carbon atoms is particularly preferable.

  Examples of the aliphatic or alicyclic alkyl (meth) acrylate having 6 or more carbon atoms include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and isooctyl (meta). ) Acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) Acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate Etc., and among them isodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate is preferably used.

  Examples of monofunctional (meth) acrylates other than (meth) acrylates of aliphatic or alicyclic alkyl having 6 or more carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycerin mono (Meth) acrylate, glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene oxide Modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, Toxiethyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) Examples include acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate.

  Among these, monofunctional (meth) acrylates that do not contain a hydroxyl group are preferable, and further, acrylates having a molecular weight of about 100 to 300 are preferable.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. , Dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified Bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pen Erythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) An acrylate etc. are mentioned.

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Examples include hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, and glycerin polyglycidyl ether poly (meth) acrylate.

  The ethylenically unsaturated monomer (B) may be used alone or in combination of two or more.

  Moreover, in this invention, it is that (A) :( B) is 10: 90-95: 5 (mass ratio) about content of the said resin (A) and an ethylenically unsaturated monomer (B). More preferably, it is preferably 50:50 to 80:20 (mass ratio). When the content of the resin (A) is less than the above range, the adhesive strength is deteriorated.

<(C) Photopolymerization initiator (radiation radical polymerization initiator)>
Examples of the radiation radical polymerization initiator (C) used in the present invention include α-diketones such as diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethyl Aminoacetophenone, α, α-dimethoxy-α-acetoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1- [2-methyl-4-methylthiophenyl] -2 Acetophenones such as morpholino-1-propanone, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; [1,2'-bisimidazole] -3,3 ' , 4,4′-tetraphenyl, [1,2′-bisimidazole] -1,2′-dichlorophenyl-3,3 ′, 4,4′-tetraphenyl and the like bisimidazoles, di-tert-butyl par Peroxides such as oxides; 2,4,6-trimethylbenzoyldiphenylphosphine oxy And acylphosphine oxides such as side.

  Commercially available products include Irgacure 184, 369, 819, 651, 500, 907, CGI369, CG24-61, OXE01, OXE02, Lucirin LR8728, Lucirin TPO, Darocur 1116, 1173 (above, BASF Corporation), Ubekril P36 ( And those commercially available under trade names such as UCB Corporation).

  Among these, Irgacure 369 (trade name), Irgacure 819 (trade name), Irgacure 784 (trade name), and their combined use with Darocur 1173 (trade name), Lucirin TPO (trade name) due to curability with irradiation light of λ = 405 nm Product name), Irgacure OXE01 (product name), and Irgacure OXE02 (product name) are preferable.

  The radiation radical polymerization initiator (C) may be used alone or in combination of two or more. The radiation radical polymerization initiator (C) is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 30 parts by mass with respect to 100 parts by mass of the resin (A). Can be used. If the amount of the radiation radical polymerization initiator (C) used is less than the above range, it is easily affected by radical deactivation (sensitivity reduction) due to oxygen, and if it is more than the above range, the compatibility may be deteriorated or stored. The stability tends to decrease.

  In the composition of the present invention, if necessary, a compound having a hydrogen donating property such as mercaptobenzothioazole or mercaptobenzoxazole, or a radiosensitizer can be used in combination with the radiation radical polymerization initiator (C). .

<Other ingredients>
The resin composition of the present invention comprises the above-described resin (A) and, if necessary, a compound (B) having at least one ethylenically unsaturated double bond and / or a radiation radical polymerization initiator (C). In addition, other components such as surfactant (D), silane coupling agent (E), colorant (F), thermal polymerization inhibitor (G), and acid anhydride (H) are contained as necessary. May be.

<(D) Surfactant>
In the resin composition of the present invention, a surfactant (D) can be blended for the purpose of improving applicability, antifoaming property, leveling property and the like. As such surfactants, for example, BM-1000, BM-1100 (above, manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (above, Dainippon Ink & Chemicals, Inc.) Manufactured), FLORARD FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S -141, S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (above, manufactured by Toray Dow Corning Silicone) Fluorosurfactants marketed under the trade name can be used.

  The compounding amount of the surfactant (D) is preferably 5 parts by mass or less with respect to 100 parts by mass of the resin (A).

<(E) Silane coupling agent>
A silane coupling agent (E) can be added to the resin composition of the present invention for the purpose of improving adhesion. As such a silane coupling agent, those having a trialkoxysilyl group are preferable, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate. Examples thereof include natopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  The silane coupling agent (E) may be used alone or in combination of two or more, and the amount used is preferably 5 parts by mass or less with respect to 100 parts by mass of the resin (A).

<(F) Colorant>
By adding a colorant (F) to the resin composition of the present invention, it is possible to easily visually confirm the amount of penetration into the coated part and the inside of the glass panel when coated on the glass panel. Such a colorant is not particularly limited, but it is soluble in the resin composition according to the present invention without using a solvent, does not fade over time, and does not overlap with the absorption wavelength of the radiation radical polymerization initiator (C). preferable.

  Of these, organic dyes are preferred. An organic dye may be used individually by 1 type, and may use 2 or more types together as needed.

  When the organic dye is added to the resin composition according to the present invention, the wavelength of maximum absorbance is preferably 450 to 750 nm, and more preferably 600 to 750 nm. As such organic dyes, oil yellow # 101, oil yellow # 130, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil blue # 613, oil black BY, oil black BS, oil black T-505 (above, manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI (Color Index Number) 42555), Methyl Violet (CI42535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue ( CI52015).

  The organic dye can be appropriately dissolved in the resin composition by a known method. Examples of such a method include a method using a high-speed stirrer such as a dissolver.

  The addition amount of the organic dye may be appropriately adjusted depending on the environment (conditions / uses) in which the resin composition is used, and is preferably 0.01 to 1% by mass of the entire resin composition, and 0.05 to 0.5% by mass. Is more preferable.

<(G) Thermal polymerization inhibitor>
If necessary, a thermal polymerization inhibitor can be added to the resin composition of the present invention as the component (G). Examples of such thermal polymerization inhibitors include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4 , 4 ′-(1-methylethylidene) bis (2-methylphenol), 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4 ′-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidene tris (2-methylphenol), 4,4 ′, 4 ″ -ethylidene tris Phenol, 1,1,3-tris (2,5-dimethyl-4-hydroxy Eniru) -3-phenyl-propane and the like.

  The amount of the thermal polymerization inhibitor used is preferably 5 parts by mass or less with respect to 100 parts by mass of the resin (A).

<(H) Acid or acid anhydride>
In the resin composition of the present invention, for example, acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid are used to finely adjust the solubility in an alkaline stripping solution. Monocarboxylic acids such as cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, Hydroxymonocarboxylic acids such as 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid Terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, Polycarboxylic acids such as lomellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, anhydrous Tricarbanilic acid, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride Acid anhydrides such as acid, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic anhydride, and glycerin tris anhydrous trimellitate may be added.

<Preparation of resin composition>
To prepare the resin composition of the present invention, the component (A), (B) and / or (C) as necessary, and the components (D), (E), (F) as necessary. , (G), (H) and other components are mixed by a known method and stirred. For example, a necessary amount of each raw material is put into a SUS preparation tank having stirring blades, and stirred at room temperature until uniform. Moreover, you may filter the composition obtained using the mesh, the membrane filter, etc. further as needed.

The resin composition thus obtained preferably has a viscosity of 0.5 to 3.0 Pa · s, more preferably 0.7 to 2.0 Pa · s, and 1.0 to 1. It is particularly preferred to have a viscosity of 8 Pa · s. By having a viscosity in this range, the penetration into the glass panel is improved, and the glass panel after etching can be prevented from being damaged. In addition, depending on the size of the gap (gap) between the glass panels, the viscosity of 0.5 Pa · s or more keeps the coating property of the resin composition well and seals the glass panel sufficiently. In addition, by setting the pressure to 3.0 Pa · s or less, it is possible to maintain good penetration into the glass panel and to prevent the glass panel from being damaged after etching. The viscosity of the resin composition is controlled by the molecular weight of the resin (A) and the mixing ratio with the ethylenically unsaturated monomer (B). Moreover, you may contain an organic solvent for the low viscosity in the range which does not impair the effect of this invention.
The resin composition of the present invention described above is excellent in hydrofluoric acid barrier properties and permeability. In particular, since the resin having an ethylenically unsaturated group can be cured by light (that is, it can be a photosensitive resin composition), the resin composition of the present invention is used when processing glass. Suitable for

<Manufacturing method of thinned glass panel>
The manufacturing method of the thinned glass panel of this invention uses the process which apply | coats the resin composition of this invention mentioned above to a glass panel outer peripheral part, and forms an outer peripheral part seal | sticker, and etching liquid, such as a hydrofluoric acid. And a step of reducing the thickness by etching. Hereinafter, the manufacturing method of the thin glass panel of this invention is demonstrated in detail for every process.

[Glass Panel Sealing Method (Process for Forming Outer Portion Seal by Applying Resin Composition to Outer Portion of Glass Panel)]
The application example as a sealing agent of the resin composition which concerns on this invention is shown below.
Two glass plates having a thickness of 0.5 to 1.0 mm are bonded to each other so that a gap of 2 to 20 μm is formed, and the resin composition is applied to the outer peripheral portion manually or using a coating device such as a dispenser. At this time, the penetration amount of the resin composition is preferably 1 to 10 mm from the outer peripheral portion.

Next, the applied resin composition is baked to remove the solvent from the coating film, thereby forming the outer peripheral sealant. When the resin composition contains a (meth) acrylate group, the resin composition is further exposed to an active energy ray such as ultraviolet light or excimer laser light to be exposed and cured. The energy dose to be irradiated varies depending on the composition of the resin composition, but is preferably 200 to 5000 mJ / cm ² , for example. Further, when the wavelength of the irradiation light is λ <400 nm, the liquid crystal layer of the glass panel is damaged. Therefore, it is preferable to cure by irradiating light of λ> 400 nm, for example, radiant light from an LED lamp of λ = 405 nm. Further, the adhesion between the resin and the glass panel can be further improved by post-baking (baking after curing).

[Glass panel etching (process of thinning by wet etching)]
Next, the glass panel is etched by dipping or showering at 20 to 80 ° C. for 30 to 200 minutes using a hydrofluoric acid-based etching solution such as hydrofluoric acid or ammonium fluoride. By this etching, the total thickness of the bonded glass plates is reduced to 0.2 to 1.0 mm.

  When the sealing treatment is performed using a conventional resin composition, the resin composition has a high viscosity (for example, about 6.0 Pa · s), so that the resin composition that could not completely penetrate into the interior of the glass panel It swells outside and builds a convex bulge. For this reason, after the etching, the convex bulge becomes thicker than the glass panel, and the glass panel is likely to be damaged.

  However, since the viscosity of the resin composition according to the present invention is low, the resin composition has high permeability and is unlikely to form a convex bulge. Therefore, the possibility of damaging the glass panel can be greatly reduced. Furthermore, when the specific monomer (B) is contained, the viscosity can be adjusted while maintaining the hydrofluoric acid barrier property and adhesion.

  Furthermore, the content of the silane coupling agent, which is essential in the conventional resin composition for sealing materials, is to be exhibited without adding a silane coupling agent that causes a residue to the resin. It has a feature that peeling and recoating are easy when a defect occurs in the outer peripheral seal.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

  [Synthesis Example 1]

・ Polybutadiene polyurethane resin [A-1]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 100 g of both ends hydroxylated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 7 g of isophorone diisocyanate, 200 g of cyclohexanone (solvent), 0.002 g of dibutyltin dilaurate (catalyst) was charged and reacted at 70 ° C. overnight to obtain a hydrogenated polybutadiene polyurethane resin [A-1] [weight average molecular weight 79,000] as a resin solution.

[Synthesis Example 2] to [Synthesis Example 5]
Resins [A-2] to [A-5] were synthesized in the same manner as in Synthesis Example 1 except that the amount of each compound was changed to the composition shown in Table 1.

・ Alkali-soluble group-introduced polybutadiene polyurethane resin [A-6]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 100 g of hydroxylated hydrogenated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 2,2-bis (hydroxyethyl) propionic acid 2.7 g, isophorone diisocyanate 18.4 g, cyclohexanone (solvent) 200 g, dibutyltin dilaurate (catalyst) 0.005 g were charged and reacted at 70 ° C. for 3 hours to give a hydrogenated polybutadiene polyurethane resin [A-6] [ Weight average molecular weight 19,000] was obtained as a resin solution.

・ Polybutadiene polyester resin [A-7]
In a flask equipped with a thermometer, a stirrer, a Dean-Stark device, and a water-cooled condenser, 100 g of both-end hydroxylated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 5.9 g of terephthaloyl chloride, 200 g of toluene (solvent), 6.9 g of pyridine (catalyst) was charged and reacted at 130 ° C. overnight to obtain a polybutadiene-based polyester resin [A-7] [weight average molecular weight 49,000].

・ (Meth) acrylate group-introduced polybutadiene polyurethane resin [A-8]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 100 g of hydroxylated hydrogenated polybutadiene (GI-3000 manufactured by Nippon Soda Co., Ltd.), 13.8 g of isophorone diisocyanate, cyclohexanone (solvent) 200 g and 0.005 g of dibutyltin dilaurate (catalyst) were added and reacted at 70 ° C. for 3 hours. Then, 3.4 g of isophorone diisocyanate and 3.6 g of 2-hydroxyethyl acrylate were added and the mixture was stirred at 70 ° C. for 3 hours. By reacting, a (meth) acrylate group-introduced polybutadiene polyurethane resin [A-8] [weight average molecular weight 17,000] was obtained as a resin solution.

Photosensitive resin composition [R-1] [Comparative Example 4]
According to Example 5 of JP 2010-106048 A (Patent Document 5), 34 g of a modified epoxy acrylate having a bisphenol A skeleton (EBECRYL 3701, manufactured by Daicel Cytec), N-acryloyloxyethyl hexahydrophthalimide (M140, manufactured by Toagosei Co., Ltd.) ) 26 g and 36 g of α-methacryloxy-γ-butyrolactone (GBLMA, manufactured by Osaka Organic Chemicals) were mixed to obtain Resin [R-1]. The compositions of Resin [A-1] to Resin [A-8] are shown in Table 1.

a-1-1: Both end hydroxyl group-hydrogenated polybutadiene GI-3000 (manufactured by Nippon Soda Co., Ltd.)
a-1-2: hydroxylated hydrogenated polybutadiene at both ends GI-1000 (manufactured by Nippon Soda Co., Ltd.)
a-1-3: Hydroxyl-terminated liquid polybutadiene R-45HT (manufactured by Idemitsu Kosan Co., Ltd.)
a-2-1: Isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
a-2-2: Hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
a-2-3: Methylenediphenyl 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
a-2-4: terephthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
b-1: 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
c-1: 2,2-bis (hydroxyethyl) propionic acid

<Evaluation of practical properties>
(1) Production of Etch Solution Resistance Evaluation Substrate Using the resins [A-1] to [A-8] according to Synthesis Examples 1 to 8 and other resins, production of a substrate was attempted as shown in Table 2. That is, in Examples 1 to 7 and Comparative Example 1 shown in Table 2, after applying the above resin solution on a silicon substrate having a thermal oxide film (SiO ₂ film thickness: 300 nm) using a spin coater. The film was baked on a hot plate at 120 ° C. for 10 minutes to remove the solvent from the coating film, thereby forming a coating film (protective film) having a thickness of 40 μm. In Comparative Examples 2 to 3, a film thickness of 40 μm was obtained in the same manner as in Example 1 except that 4% by mass of p-toluenesulfonic acid was added as a thermosetting catalyst to the resin liquid, and the baking conditions were changed to 220 ° C. for 5 minutes. A coating film (protective film) was formed. In Examples 8 to 10, an ethylenically unsaturated monomer (B) (127 parts by mass with respect to 100 parts by mass of the resin (A)) and a photopolymerization initiator (C) (resin ( A) and (B) 3 parts by mass with respect to the total of 100 parts by mass of the component (B), a coating film having a film thickness of 40 μm was formed in the same manner as in Example 1, and 2J ultraviolet rays were used using a high-pressure mercury lamp. The coating film (protective film) was cured by exposing to (wavelength 365 nm conversion). The surface tackiness of the protective film was confirmed by touching with a finger. When tackiness was observed, “Yes” was indicated, and when it was not recognized, “No” was indicated.

(2) Etching solution (hydrofluoric acid solution) resistance After the substrate with the protective film prepared by the above method is immersed in a 20% aqueous hydrofluoric acid solution at 25 ° C. for 1 hour, the protective film is physically peeled off to form a protective film. The film thickness of the covered thermal oxide film was measured using an ellipsometer (JA Woollam M-2000). The case where the thickness of the thermal oxide film was 290 nm or more was “◎”, the case where it was 200 nm or more and less than 290 nm was “◯”, and the case where it was less than 200 nm was “X”.

(3) Acid / Alkali Resistance In the same manner as the etching solution resistance, the film was immersed in an acidic aqueous solution or an alkaline aqueous solution described in Table 3 for 1 hour, then washed with water and dried. When the protective film was observed to be altered, such as swelling, dissolution, or peeling, it was rated as “x”, and when it was not observed, it was marked as “◯”.

(4) Production of glass panel with seal on outer periphery Two glass plates having a thickness of 1.0 mm were bonded together with a spacer having a thickness of 10 μm interposed therebetween to produce a glass panel having a gap of 10 μm. The resin composition of the present invention (Example 9) having a viscosity of 1250 mPa · s at 25 ° C. was manually applied to the outer peripheral portion of this glass panel, and then 2J ultraviolet rays (wavelength 365 nm conversion) using a high-pressure mercury lamp. The resin composition (peripheral part seal) was cured by exposing to. Furthermore, the outer peripheral part seal swelled outside the glass panel was manually peeled off to produce a glass panel with an outer peripheral part seal.

(5) Glass panel etching (thinning)
The glass panel with an outer peripheral part seal produced by the above-mentioned method was immersed in a 20% aqueous solution of hydrofluoric acid at 40 ° C. for 1 hour, washed with water and dried. A photograph of the outer periphery of the glass panel viewed from the side is shown in FIG.

UC-203: Kuraray-made methacryloyl-modified liquid isoprene rubber V-4221: DIC Corporation polyester polyurethane G-3000: Nippon Soda Co., Ltd. both terminal hydroxyl group polybutadiene R-45HT: Idemitsu Kosan group hydroxyl group-terminated liquid polybutadiene B-1: Isodecyl acrylate (Sartomer)
C-1: Irgacure 907 (BASF)

  From Table 2, the following can be said. Since the resin of the present invention does not contain a silane coupling agent and has good substrate adhesion, it adheres to the substrate even after etching, and also has excellent hydrofluoric acid barrier properties. On the other hand, polyurethane resin that is not polybutadiene (Comparative Example 1) has good adhesion, but does not have hydrofluoric acid barrier properties. Moreover, even if it is a polybutadiene type, when there is no hydrogen bond formed by a urethane bond or an ester bond, a hydrofluoric acid barrier property cannot be obtained (Comparative Examples 2 and 3). Since the resin of the present invention is soft, tackiness may remain on the film surface after baking, but the tackiness can be controlled by the amount of hydrogen bonds. That is, if the amount of the sites forming hydrogen bonds such as urethane bonds and carboxylic acid groups is increased, the film becomes hard and surface tackiness can be eliminated. On the other hand, when the hydrogen bond is weak or the amount of hydrogen bond is small, the hydrofluoric acid barrier property is slightly reduced (Examples 7 and 10). In Japanese Patent Application Laid-Open No. 2010-106048, the softening point is preferably 60 ° C. or more from the viewpoint of heat resistance, but the resin of the present invention has no problem even in an etching process at 40 ° C.

  Further, as shown in Table 3, the protective film of the present invention exhibits good resistance without deterioration even in a high concentration acidic aqueous solution or alkaline aqueous solution. In particular, a general resin protective film is dissolved in concentrated nitric acid having a concentration of 70%, but the protective film of the present invention maintains good substrate adhesion without deterioration. In addition, the protective film (Example 9) containing the ethylenically unsaturated monomer (D) for the purpose of reducing the viscosity has reduced nitric acid resistance, and after the temporary immersion, the protective film peeled off from the substrate. After immersion for 30 minutes, no alteration such as peeling was observed. In addition, resistance to other acids such as hydrofluoric acid did not decrease.

  Further, as shown in FIG. 1, the protective material of the present invention penetrates well into the gaps of the glass panel, and the portion raised to the outside can be easily removed. Even after the etching process at 40 ° C., neither swelling nor penetration of the etching solution is observed, and the protective material is the portion immersed in the etching solution (the portion after thinning) and the portion not immersed (the initial glass thickness portion). The deterioration of was not seen.

Claims (13)

  A composition comprising a resin obtained by reacting a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol with a crosslinking agent (a2) as a component (A). A method for producing a glass substrate thinned by etching, comprising: a step of applying to an outer peripheral portion to form an outer peripheral seal; and a step of thinning by etching.   The method for producing a substrate according to claim 1, wherein the reaction between the polyol (a1) and the crosslinking agent (a2) is an ester bond forming reaction.   The method for producing a substrate according to claim 1, wherein the reaction between the polyol (a1) and the crosslinking agent (a2) is a urethane bond forming reaction.   The said polyol (a1) is hydrogenated polybutadiene polyol, The manufacturing method of the board | substrate as described in any one of Claims 1-3 characterized by the above-mentioned.   The method for producing a substrate according to claim 1, wherein the resin of the component (A) further comprises a (meth) acrylate group.   The method for producing a substrate according to claim 1, wherein the resin as the component (A) further has an alkali-soluble group.   The said composition contains the (B) ethylenically unsaturated monomer further, The manufacturing method of the board | substrate as described in any one of Claims 1-6 characterized by the above-mentioned.   The method for producing a substrate according to claim 7, wherein the ethylenically unsaturated monomer is an aliphatic or alicyclic alkyl (meth) acrylate having 6 or more carbon atoms.   The said composition contains the (C) photoinitiator further, The manufacturing method of the board | substrate as described in any one of Claims 1-8 characterized by the above-mentioned.   The method for manufacturing a substrate according to claim 1, wherein the etching is wet etching.   A substrate manufactured by the manufacturing method according to claim 1.   An electronic component comprising the substrate according to claim 11.   The component (A) includes a resin obtained by reacting a polyol (a1) selected from polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol with a crosslinking agent (a2). Resin composition for glass processing.

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