WO2015159769A1 - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
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- WO2015159769A1 WO2015159769A1 PCT/JP2015/060930 JP2015060930W WO2015159769A1 WO 2015159769 A1 WO2015159769 A1 WO 2015159769A1 JP 2015060930 W JP2015060930 W JP 2015060930W WO 2015159769 A1 WO2015159769 A1 WO 2015159769A1
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- Prior art keywords
- acrylate
- meth
- resin composition
- curable resin
- conjugated diene
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
Definitions
- the present invention is solvent-free and cured by irradiation with active energy rays or heating, and the cured product has excellent heat yellowing resistance, excellent optical transparency, and does not cause peeling over time with respect to a substrate.
- the present invention relates to a curable resin composition suitable for various uses such as pressure-sensitive adhesives, adhesives and coating agents.
- an active energy ray-curable adhesive As an adhesive capable of improving the production efficiency of the product, for example, an active energy ray-curable adhesive is known. Since the active energy ray-curable pressure-sensitive adhesive usually does not contain a solvent such as a solvent or water, it does not require a step of removing the solvent when forming the pressure-sensitive adhesive layer. Examples of the pressure-sensitive adhesive having a level of adhesive strength that can be used in the production of the IT product and the like and capable of improving the production efficiency of the final product as compared with the conventional products include, for example, a polymer 20 having two or more acrylate groups. A pressure-sensitive adhesive composition characterized by comprising ⁇ 80% by mass, plasticizer 20 ⁇ 80% by mass, acrylate monomer 0 ⁇ 30% by mass and further a photopolymerization initiator is known. (See Patent Document 1).
- An object of the present invention is to provide a curable resin composition that is excellent in moderate adhesion and transparency and that can provide a cured product having good heat yellowing resistance.
- a curable resin composition containing (A) a conjugated diene polymer polyol and (B) a compound having a (meth) acrylate group is a first gist.
- the (A) conjugated diene polymer polyol preferably has a 1,2-butadiene skeleton.
- the compound (B) having a (meth) acrylate group reacts with at least a polymer polyol (a) having a hydroxyl group in the molecule and a (meth) acrylate having a substituent that reacts with a hydroxyl group. It is preferable that it is a compound obtained by making it.
- the present inventors provide a curable resin composition for obtaining a cured product having excellent heat-resistant yellowing, excellent optical transparency, and exhibiting a level of tackiness that does not cause peeling over time with respect to a substrate.
- earnest research was repeated.
- the intended purpose can be achieved by a curable resin composition containing a predetermined (A) conjugated diene polymer polyol and (B) a compound having a (meth) acrylate group in the course of the research. And the present invention has been reached.
- a curable resin composition for obtaining a cured product having excellent heat-resistant yellowing resistance, excellent optical transparency, and exhibiting a level of tackiness that does not cause peeling over time with respect to a substrate. I can do it.
- the conjugated diene polymer polyol used in the present invention is not particularly limited, and specifically, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol can be used. Considering the availability of industrial products, polybutadiene polyol is preferable.
- the number average molecular weight of the conjugated diene polymer polyol is not particularly limited, but is preferably 500 or more and 40000 or less. If the viscosity is less than 500, the viscosity is too low and the cured product may flow, and if it exceeds 40000, the production of the curable resin composition becomes difficult.
- the content of the conjugated diene polymer polyol (A) of the present invention is preferably 1% by mass or more and 95% by mass or less, more preferably 2% by mass or more and 90% by mass with respect to 100% by mass of the curable resin composition. It is more preferably 3% by mass or more and 85% by mass.
- the amount is less than 1% by mass, the effect on the cured product is small, and when it exceeds 95% by mass, the curability is significantly deteriorated.
- the compound having a (B) (meth) acrylate group of the present invention is not particularly limited.
- the compound obtained by making acrylate react is mentioned.
- (B1) a urethane (meta) obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule, a polyisocyanate (b), and a (meth) acrylate (c) having a hydroxyl group in the molecule.
- urethane (meth) acrylate Acrylate (hereinafter referred to as urethane (meth) acrylate), (B2) a polymer obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule and (meth) acrylate (d) having an isocyanate group, And (B3) a polymer polyol obtained by a reaction of a polymer polyol (a) having a hydroxyl group in the molecule with an acrylate (e) having a carboxyl group such as acrylic acid.
- urethane (meth) acrylate Acrylate (hereinafter referred to as urethane (meth) acrylate)
- B2 a polymer obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule and (meth) acrylate (d) having an isocyanate group
- B3 a polymer polyol obtained by a reaction of a polymer polyol
- (B4) a conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene and isoprene, After reacting the dibasic unsaturated acid anhydride (g), subsequently, (meth) acrylate having a hydroxyl group in the molecule in part or all of the acid anhydride residue in the obtained prepolymer
- a conjugated diene polymer obtained by reacting (c), (B5) an acrylic ester (h) obtained by modifying an aliphatic alcohol, and the like.
- the polymer polyol (a) having a hydroxyl group is not particularly limited, and specifically, a polyester polyol, a polycarbonate polyol, a polyether polyol, an aliphatic hydrocarbon polyol, and an alicyclic hydrocarbon polyol can be used. .
- polyether polyol is particularly preferable because it is easy to produce and excellent in various performances.
- the polyether polyol is not particularly limited, and polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol can be used. From the viewpoints of heat resistance of the cured product, flexibility and viscosity of the curable resin composition, among the polyether polyols, a poly-polyether containing a polyether chain portion obtained by ring-opening polymerization of propylene oxide, butylene oxide or tetrafluoroethylene is particularly preferred. Ether polyols are preferred.
- the number average molecular weight of the polymer polyol (a) having a hydroxyl group is not particularly limited, but is preferably 500 or more and 20000 or less. If it is less than 500, hardened
- the polyisocyanate (b) is not particularly limited, and specific examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.
- Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 , 5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like.
- alicyclic polyisocyanates examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Can be mentioned.
- Aromatic polyisocyanates include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5 -Naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.
- MDI 4,4′-diphenylmethane diisocyanate
- araliphatic polyisocyanate examples include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate, and the like.
- modified bodies such as a dimer, a trimer of these organic polyisocyanate, and a buret-ized isocyanate, can be mentioned. These may be used alone or in combination of two or more.
- Hexamethylene diisocyanate is preferable from the viewpoint of lowering the viscosity, and isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate should be used from the viewpoint of heat-resistant yellowing. Is preferred.
- the (meth) acrylate (c) having a hydroxyl group in the molecule is not particularly limited. Specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4 -Hydroxybutyl acrylate, caprolactone-modified-2-hydroxyethyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol monoacrylate, polybutylene glycol mono (meth) acrylate, 2- (meth) acryloyloxy Ethyl-2-hydroxyethyl phthalate, phenyl glycidyl ether (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, potassium Rorakuton modified dipentaerythritol penta (meth) acrylate and the like, can be used in combination singly used or
- the (meth) acrylate (d) having an isocyanate group is not particularly limited, and specific examples include 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate. These can be used alone or in combination.
- the acrylate (e) having a carboxyl group such as acrylic acid is not particularly limited. Specifically, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthal An acid, acrylic acid, etc. are mentioned. These can be used alone or in combination.
- the conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene is, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenylbutadiene, 2 -Phenylbutadiene, 1,1-diphenylbutadiene, 1,2-diphenylbutadiene, 2,3-diphenylbutadiene and the like.
- the conjugated diene polymer may be composed of one kind of these conjugated diene compounds or may be composed of two or more kinds.
- conjugated diene prepolymer polybutadiene, polyisoprene, or a copolymer of a mixture of isoprene and butadiene is particularly preferable.
- Conjugated diene prepolymers are prepared by using the above conjugated diene compounds such as butadiene and isoprene as initiators such as sodium naphthalene complex, n-butyllithium, s-butyllithium, methyllithium, ethyllithium, and alkyllithium such as pentyllithium.
- It can also be produced by anionic polymerization, or by radical polymerization using an azobisnitrile compound such as azobisisobutyronitrile and a peroxide such as benzoyl peroxide as an initiator.
- azobisnitrile compound such as azobisisobutyronitrile
- a peroxide such as benzoyl peroxide
- These polymerization reactions are usually performed under the conditions of a polymerization temperature of ⁇ 80 ° C. to 150 ° C. and a polymerization time of 1 to 100 hours in the presence of an aliphatic or aromatic hydrocarbon solvent such as hexane, heptane, toluene, and xylene.
- the number average molecular weight of the compound is not particularly limited, but is preferably 500 or more and 80000 or less. If it is less than 500, the synthesis is difficult, and if it exceeds 80000, the viscosity becomes high and it becomes difficult to use.
- the dibasic unsaturated acid anhydride (g) is not particularly limited, and specific examples include phthalic anhydride, phthalic anhydride, pyromellitic anhydride, and tetracarboxylic anhydride. These can be used alone or in combination.
- the acrylic ester (h) obtained by modifying the aliphatic alcohol is not particularly limited, but specific examples include 3,3,5-trimethylcyclohexane (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth).
- lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and 1,9-nonanediol di (meth) acrylate are preferable from the viewpoint of low viscosity and low odor.
- the urethane (meth) acrylate (B1) can be synthesized by a known method. For example, a predetermined amount of component (b) is added to an excessive amount of component (a) and reacted at 80 ° C. until a predetermined amount of free isocyanate is obtained to obtain polyurethane, and further at 70-80 ° C., further hydroquinone monomethyl In the presence of a polymerization inhibitor such as ether, the component (c) can be charged all at once and heated and stirred at 70 to 80 ° C. until free isocyanate disappears. At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.
- a tin-based catalyst such as dibutyltin dilaurate may be added.
- the number of functional groups of polyurethane obtained by reacting (a) and (b) is 1.0 or more and 4.0 or less.
- the number of functional groups is less than 1.0, the cured product has fluidity and may flow out with time, and when it exceeds 4.0, the cured product becomes too hard.
- the ratio of (c) is 1.0 to 2.0 molar ratio with respect to (b)-(a), but 1.0 to 1.5 molar ratio is preferable.
- the compound obtained by reacting the polymer polyol (a) having a hydroxyl group in the molecule (B2) and the (meth) acrylate (d) having an isocyanate group can be synthesized by a known method. For example, it can be synthesized by charging a predetermined amount of the component (a), charging the component (d) all together, and heating and stirring at 70 to 80 ° C. until free isocyanate is eliminated. At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.
- the polymer polyol obtained by the reaction of the polymer polyol (a) having a hydroxyl group in the molecule (B3) and the acrylate (e) having a carboxyl group such as acrylic acid can be synthesized by a known method. is there. For example, it can be obtained by adding a predetermined amount of component (a), adding an excessive amount of (e), and performing a dehydration esterification reaction using a catalyst such as paratoluenesulfonic acid. In this case, the reaction can be usually carried out in the presence of an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene, cyclohexane and the like, under conditions of a dehydration esterification temperature of 70 ° C. to 150 ° C. and a reaction time of 1 to 20 hours.
- an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene, cyclohexane and the like
- a conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene is reacted with a dibasic unsaturated acid anhydride (g) and then obtained.
- the conjugated diene polymer obtained by reacting a part or all of the acid anhydride residue in the prepolymer with a (meth) acrylate (c) having a hydroxyl group in the molecule is a commercially available product.
- trade names manufactured by Kuraray Co., Ltd .: Claprene UC-102, UC-203, and the like can be mentioned.
- the content of the compound having a (B) (meth) acrylate group of the present invention is preferably 1% by mass or more and 99% by mass or less, more preferably 10% by mass with respect to 100% by mass of the curable resin composition. It is 98 mass% or less, More preferably, it is 20 mass% or more and 97 mass% or less. If it is less than 1% by mass, the curability may be deteriorated. If it exceeds 99% by mass, it may be yellowed after the heat resistance test.
- the curable resin composition of this invention adds the polymerization initiator by an active energy ray as needed.
- the polymerization initiator by active energy rays here includes both a photopolymerization initiator and a polymerization initiator by active energy rays such as ultraviolet rays.
- aromatic ketones such as benzophenone
- aromatic compounds such as anthracene and ⁇ -chloromethylnaphthalene
- sulfur compounds such as diphenyl sulfide and thiocarbamate
- polymerization initiators using active energy rays such as ultraviolet rays other than visible light include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and xanthone.
- Product name: Kayacure DETX etc. can be mentioned.
- the content of these polymerization initiators varies depending on the type and the like, but as a guide, it is 1 to 8 parts by mass with respect to 100 parts by mass of the curable resin composition.
- the energy ray source for curing the curable resin composition of the present invention is not particularly limited, and examples thereof include a high pressure mercury lamp, an electron beam, a ⁇ ray, a carbon arc lamp, a xenon lamp, and a metal halide lamp.
- cured by heating it can be cured by heating to a temperature range of 60 to 250 ° C.
- additives usually contained in paints, coating agents, and the like can be added to the curable resin composition of the present invention as necessary.
- the additive include a light stabilizer, an ultraviolet absorber, a catalyst, an antifoaming agent, a polymerization accelerator, an antioxidant, a flame retardant, an infrared absorber, an antistatic agent, a plasticizer, and a dispersant.
- the curable resin composition of the present invention described in detail above has performance such as adhesiveness and heat-resistant yellowing, it can be used for electronic terminals such as mobile phones, electronic books, touch panels, liquid crystal televisions, plasma televisions, organic EL televisions, etc. It can be used as a filler for the space between the display panel of the display device and the protective plate.
- (B-6) Composition having a (meth) acrylate group [trade name “New Frontier L-C9A” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
- (B-7) Composition having (meth) acrylate group [trade name “ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.]
- (A-1) Conjugated diene polymer polyol [trade name “NISSO-PB G-1000” manufactured by Nippon Soda Co., Ltd.]
- (A-2) Conjugated diene polymer polyol [trade name ⁇ “Polybd R-45HT” manufactured by Idemitsu Kosan Co., Ltd.]
- (A-3) Conjugated diene polymer polyol [trade name “Krasol LBH3000” manufactured by Cray Valley]
- the curable resin composition was dropped on a glass having a predetermined size in which 300 ⁇ m spacers were arranged on four sides, filled in a glass plate, and a glass plate having the same size was covered from above. Next, using a high-pressure mercury lamp 80 W / cm, it was irradiated with an integrated illuminance of 5000 mJ / cm @ 2 in an air atmosphere and cured to obtain a cured product.
- ⁇ transparency ⁇ The curable resin composition was visually observed, and a transparent one was evaluated as ⁇ and a white haze was evaluated as x.
- ⁇ Heat-resistant ⁇ The cured product (cured film) was heated in an oven at 110 ° C. for 500 hours. The cured product did not flow and the cured product flowed. [Heat-resistant yellowing] The cured product (cured film) was heated in an oven at 110 ° C. for 500 hours, and the discoloration after the heating was measured for YI value using a Spectrophotometer SD6000 manufactured by Nippon Denshoku Industries Co., Ltd. A sample having a measured YI of less than 4 was evaluated as ⁇ , and a sample having a YI of 4 or more was evaluated as ⁇ .
- a cured product (cured film) obtained by curing the curable resin composition of the present invention was able to obtain a cured product excellent in transparency and heat yellowing resistance. From Comparative Example 1, it was confirmed that the cured product using the curable resin composition containing no conjugated diene polymer polyol was inferior in heat yellowing. From Comparative Example 2, it was confirmed that the cured product using the curable resin composition not containing a compound having a (meth) acrylate group was inferior in heat resistance. Further, in the conjugated diene polymer polyol and the composition having a (meth) acrylate group described in Examples 1 to 7, when the curable resin composition is used, transparency and heat-resistant yellowing similar to those in Examples are used. It has been confirmed that a cured product having excellent resistance is obtained.
- the curable resin composition of the present invention has performances such as adhesiveness and heat-resistant yellowing, display of a display device such as an electronic terminal such as a mobile phone, an electronic book or a touch panel, a liquid crystal television, a plasma television, or an organic EL television. It can be used as a filler for the space between the panel and the protective plate.
- a display device such as an electronic terminal such as a mobile phone, an electronic book or a touch panel, a liquid crystal television, a plasma television, or an organic EL television. It can be used as a filler for the space between the panel and the protective plate.
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Abstract
Provided is a curable resin composition for obtaining a cured product with excellent optical transparency and excellent resistance to heat-induced yellowing and which exhibits enough tackiness such that peeling from the substrate over time does not occur. A curable resin composition characterized in comprising (A) a conjugated diene polymer polyol and (B) a compound with a (meth)acrylate group. It is preferable that the conjugated diene polymer polyol (A) has a 1,2-butadiene backbone and that the compound (B) with a (meth)acrylate group comprises a polyether polyol.
Description
本発明は、無溶剤であって活性エネルギー線照射又は加熱により硬化し、その硬化物が耐熱黄変性に優れ、光学透明性に優れ、基材に対して経時的な剥離を起こさないレベルの粘着性を示すため、粘着剤、接着剤およびコーティング剤などの様々な用途に適する硬化性樹脂組成物に関する。
The present invention is solvent-free and cured by irradiation with active energy rays or heating, and the cured product has excellent heat yellowing resistance, excellent optical transparency, and does not cause peeling over time with respect to a substrate. The present invention relates to a curable resin composition suitable for various uses such as pressure-sensitive adhesives, adhesives and coating agents.
液晶ディスプレイをはじめとするいわゆるＩＴ関連製品には、その高機能化等にともなって、様々な種類の材質や形状からなる部材が多数使用されている。
前記したような部材の貼り合わせや表面被覆には、従来から粘着剤やコーティング剤が使用されている。
その中で、前記ＩＴ関連製品の製造場面では、近年、最終製品の生産性向上が大きな課題とされている。
これは、従来から使用されている粘着剤が、通常、溶剤や水等の溶媒を含むものであるため、該粘着剤を基材表面等に塗布した後、該粘着剤中に含まれる溶媒を除去する工程に多くの時間を要し、最終製品の生産効率を低下させる一因となっていたためである。
前記製品の生産効率を向上可能な粘着剤としては、例えば活性エネルギー線硬化型粘着剤が知られている。
前記活性エネルギー線硬化型粘着剤は、通常、溶剤や水等の溶媒を含まないため、粘着剤層を形成する際に、それら溶媒を除去する工程を要しないという特徴がある。
前記ＩＴ製品等の製造に使用可能なレベルの粘着力を有し、かつ、従来と比較して最終製品の生産効率を向上可能な粘着剤としては、例えば２個以上のアクリレート基を有するポリマー２０～８０質量％と、可塑剤２０～８０質量％と、アクリレート系モノマー０～３０質量％と更に光重合開始剤を含むことを特徴とする粘着剤組成物が知られている。（特許文献１参照）。 In so-called IT-related products such as liquid crystal displays, a large number of members made of various types of materials and shapes are used in accordance with their higher functions.
Conventionally, pressure-sensitive adhesives and coating agents have been used for bonding and surface coating of members as described above.
Among them, in the manufacturing scene of the IT related products, in recent years, improvement of productivity of final products has been a major issue.
This is because a conventionally used pressure-sensitive adhesive usually contains a solvent such as a solvent or water, so that the solvent contained in the pressure-sensitive adhesive is removed after the pressure-sensitive adhesive is applied to the surface of the substrate. This is because a lot of time is required for the process, which is a cause of reducing the production efficiency of the final product.
As an adhesive capable of improving the production efficiency of the product, for example, an active energy ray-curable adhesive is known.
Since the active energy ray-curable pressure-sensitive adhesive usually does not contain a solvent such as a solvent or water, it does not require a step of removing the solvent when forming the pressure-sensitive adhesive layer.
Examples of the pressure-sensitive adhesive having a level of adhesive strength that can be used in the production of the IT product and the like and capable of improving the production efficiency of the final product as compared with the conventional products include, for example, a polymer 20 having two or more acrylate groups. A pressure-sensitive adhesive composition characterized by comprising ˜80% by mass, plasticizer 20˜80% by mass, acrylate monomer 0˜30% by mass and further a photopolymerization initiator is known. (See Patent Document 1).
前記したような部材の貼り合わせや表面被覆には、従来から粘着剤やコーティング剤が使用されている。
その中で、前記ＩＴ関連製品の製造場面では、近年、最終製品の生産性向上が大きな課題とされている。
これは、従来から使用されている粘着剤が、通常、溶剤や水等の溶媒を含むものであるため、該粘着剤を基材表面等に塗布した後、該粘着剤中に含まれる溶媒を除去する工程に多くの時間を要し、最終製品の生産効率を低下させる一因となっていたためである。
前記製品の生産効率を向上可能な粘着剤としては、例えば活性エネルギー線硬化型粘着剤が知られている。
前記活性エネルギー線硬化型粘着剤は、通常、溶剤や水等の溶媒を含まないため、粘着剤層を形成する際に、それら溶媒を除去する工程を要しないという特徴がある。
前記ＩＴ製品等の製造に使用可能なレベルの粘着力を有し、かつ、従来と比較して最終製品の生産効率を向上可能な粘着剤としては、例えば２個以上のアクリレート基を有するポリマー２０～８０質量％と、可塑剤２０～８０質量％と、アクリレート系モノマー０～３０質量％と更に光重合開始剤を含むことを特徴とする粘着剤組成物が知られている。（特許文献１参照）。 In so-called IT-related products such as liquid crystal displays, a large number of members made of various types of materials and shapes are used in accordance with their higher functions.
Conventionally, pressure-sensitive adhesives and coating agents have been used for bonding and surface coating of members as described above.
Among them, in the manufacturing scene of the IT related products, in recent years, improvement of productivity of final products has been a major issue.
This is because a conventionally used pressure-sensitive adhesive usually contains a solvent such as a solvent or water, so that the solvent contained in the pressure-sensitive adhesive is removed after the pressure-sensitive adhesive is applied to the surface of the substrate. This is because a lot of time is required for the process, which is a cause of reducing the production efficiency of the final product.
As an adhesive capable of improving the production efficiency of the product, for example, an active energy ray-curable adhesive is known.
Since the active energy ray-curable pressure-sensitive adhesive usually does not contain a solvent such as a solvent or water, it does not require a step of removing the solvent when forming the pressure-sensitive adhesive layer.
Examples of the pressure-sensitive adhesive having a level of adhesive strength that can be used in the production of the IT product and the like and capable of improving the production efficiency of the final product as compared with the conventional products include, for example, a polymer 20 having two or more acrylate groups. A pressure-sensitive adhesive composition characterized by comprising ˜80% by mass, plasticizer 20˜80% by mass, acrylate monomer 0˜30% by mass and further a photopolymerization initiator is known. (See Patent Document 1).
しかしながら、前記粘着剤組成物は長期間高温に曝されると、硬化物が黄変し透明性がそこなわれる恐れがある。
本発明の目的は、適度な密着性および透明性に優れ、耐熱黄変性が良好な硬化物を得られる硬化型樹脂組成物を提供することにある。 However, when the pressure-sensitive adhesive composition is exposed to a high temperature for a long period of time, the cured product may turn yellow and transparency may be impaired.
An object of the present invention is to provide a curable resin composition that is excellent in moderate adhesion and transparency and that can provide a cured product having good heat yellowing resistance.
本発明の目的は、適度な密着性および透明性に優れ、耐熱黄変性が良好な硬化物を得られる硬化型樹脂組成物を提供することにある。 However, when the pressure-sensitive adhesive composition is exposed to a high temperature for a long period of time, the cured product may turn yellow and transparency may be impaired.
An object of the present invention is to provide a curable resin composition that is excellent in moderate adhesion and transparency and that can provide a cured product having good heat yellowing resistance.
(Ａ)共役ジエン系ポリマーポリオール、及び(Ｂ)（メタ）アクリレート基を有する化合物を含有することを特徴とする硬化性樹脂組成物を第１の要旨とする。
また、本発明は、前記（Ａ)共役ジエン系ポリマーポリオールが、１，２－ブタジエン骨格を有することが好ましい。
さらに、本発明は、前記（Ｂ）（メタ）アクリレート基を有する化合物が、少なくとも、分子中にヒドロキシル基を有するポリマーポリオール（ａ）、および水酸基と反応する置換基を有する（メタ）アクリレートを反応させて得られる化合物であることが好ましい。 A curable resin composition containing (A) a conjugated diene polymer polyol and (B) a compound having a (meth) acrylate group is a first gist.
In the present invention, the (A) conjugated diene polymer polyol preferably has a 1,2-butadiene skeleton.
Further, in the present invention, the compound (B) having a (meth) acrylate group reacts with at least a polymer polyol (a) having a hydroxyl group in the molecule and a (meth) acrylate having a substituent that reacts with a hydroxyl group. It is preferable that it is a compound obtained by making it.
また、本発明は、前記（Ａ)共役ジエン系ポリマーポリオールが、１，２－ブタジエン骨格を有することが好ましい。
さらに、本発明は、前記（Ｂ）（メタ）アクリレート基を有する化合物が、少なくとも、分子中にヒドロキシル基を有するポリマーポリオール（ａ）、および水酸基と反応する置換基を有する（メタ）アクリレートを反応させて得られる化合物であることが好ましい。 A curable resin composition containing (A) a conjugated diene polymer polyol and (B) a compound having a (meth) acrylate group is a first gist.
In the present invention, the (A) conjugated diene polymer polyol preferably has a 1,2-butadiene skeleton.
Further, in the present invention, the compound (B) having a (meth) acrylate group reacts with at least a polymer polyol (a) having a hydroxyl group in the molecule and a (meth) acrylate having a substituent that reacts with a hydroxyl group. It is preferable that it is a compound obtained by making it.
すなわち、本発明者らは、耐熱黄変性に優れ、光学透明性に優れ、基材に対して経時的な剥離を起こさないレベルの粘着性を示す硬化物を得るための硬化型樹脂組成物を得るために、鋭意研究を重ねた。その研究の過程で所定の(Ａ)共役ジエン系ポリマーポリオール、及び(Ｂ)（メタ）アクリレート基を有する化合物を含有することを特徴とする硬化性樹脂組成物により、所期の目的が達成できることを見いだし、本発明に到達した。
That is, the present inventors provide a curable resin composition for obtaining a cured product having excellent heat-resistant yellowing, excellent optical transparency, and exhibiting a level of tackiness that does not cause peeling over time with respect to a substrate. In order to obtain it, earnest research was repeated. The intended purpose can be achieved by a curable resin composition containing a predetermined (A) conjugated diene polymer polyol and (B) a compound having a (meth) acrylate group in the course of the research. And the present invention has been reached.
本発明によれば、耐熱黄変性に優れ、光学透明性に優れ、基材に対して経時的な剥離を起こさないレベルの粘着性を示す硬化物を得るための硬化性樹脂組成物を提供することが出来る。
According to the present invention, there is provided a curable resin composition for obtaining a cured product having excellent heat-resistant yellowing resistance, excellent optical transparency, and exhibiting a level of tackiness that does not cause peeling over time with respect to a substrate. I can do it.
つぎに、本発明の実施の形態を詳しく説明する。
Next, an embodiment of the present invention will be described in detail.
本発明で使用する共役ジエン系ポリマーポリオールは特には限定されないが具体的には、ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリブタジエンポリオール、水添ポリイソプレンポリオールを使用することができる。
工業品の入手しやすさを考慮するとポリブタジエンポリオールが好ましい。 The conjugated diene polymer polyol used in the present invention is not particularly limited, and specifically, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol can be used.
Considering the availability of industrial products, polybutadiene polyol is preferable.
工業品の入手しやすさを考慮するとポリブタジエンポリオールが好ましい。 The conjugated diene polymer polyol used in the present invention is not particularly limited, and specifically, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol can be used.
Considering the availability of industrial products, polybutadiene polyol is preferable.
前記共役ジエン系ポリマーポリオールの数平均分子量は特に限定されないが５００以上４００００以下が好ましい。５００未満であれば粘度が低すぎるため硬化物から流動する恐れがあり、４００００を超える場合は硬化性樹脂組成物の製造が困難となる。
The number average molecular weight of the conjugated diene polymer polyol is not particularly limited, but is preferably 500 or more and 40000 or less. If the viscosity is less than 500, the viscosity is too low and the cured product may flow, and if it exceeds 40000, the production of the curable resin composition becomes difficult.
本発明の（Ａ）の共役ジエン系ポリマーポリオールの含有量は、当該硬化型樹脂組成物の１００質量％に対して、１質量％以上９５質量％以下が好ましく、より好ましくは２質量％以上９０質量％で、更に好ましくは、３質量％以上８５質量％である。
１質量％未満の場合では、硬化物への効果が少なく、９５質量％超えの場合は、硬化性が著しく悪くなる。 The content of the conjugated diene polymer polyol (A) of the present invention is preferably 1% by mass or more and 95% by mass or less, more preferably 2% by mass or more and 90% by mass with respect to 100% by mass of the curable resin composition. It is more preferably 3% by mass or more and 85% by mass.
When the amount is less than 1% by mass, the effect on the cured product is small, and when it exceeds 95% by mass, the curability is significantly deteriorated.
１質量％未満の場合では、硬化物への効果が少なく、９５質量％超えの場合は、硬化性が著しく悪くなる。 The content of the conjugated diene polymer polyol (A) of the present invention is preferably 1% by mass or more and 95% by mass or less, more preferably 2% by mass or more and 90% by mass with respect to 100% by mass of the curable resin composition. It is more preferably 3% by mass or more and 85% by mass.
When the amount is less than 1% by mass, the effect on the cured product is small, and when it exceeds 95% by mass, the curability is significantly deteriorated.
本発明の（Ｂ）（メタ）アクリレート基を有する化合物は、特に限定されないが、例えば、少なくとも、分子中にヒドロキシル基を有するポリマーポリオール（ａ）、および水酸基と反応する置換基を有する（メタ）アクリレートを反応させて得られる化合物が挙げられる。
具体的には、（Ｂ１）分子中にヒドロキシル基を有するポリマーポリオール（ａ）、ポリイソシアネート（ｂ）、及び分子中に水酸基を有する（メタ）アクリレート（ｃ）を反応させて得られるウレタン（メタ）アクリレート（以下、ウレタン（メタ）アクリレートという。）、（Ｂ２）分子中にヒドロキシル基を有するポリマーポリオール（ａ）、及びイソシアネート基を有する（メタ）アクリレート（ｄ）を反応させて得られる化合物、および（Ｂ３）分子中にヒドロキシル基を有するポリマーポリオール（ａ）とアクリル酸などのカルボキシル基を有するアクリレート（ｅ）との反応で得られるポリマーポリオール、等が挙げられる。
上記のほかに、本発明の（Ｂ）（メタ）アクリレート基を有する化合物としては、（Ｂ４）ブタジエン、イソプレンなどの共役ジエン化合物をアニオン重合して得られる共役ジエン系プレポリマー（ｆ）に、二塩基性不飽和酸無水物（ｇ）を反応させた後、引き続き、得られたプレポリマー中の酸無水物残基の一部、または、全部に、分子中に水酸基を有する（メタ）アクリレート（ｃ）を反応させることにより得られる共役ジエン系ポリマー、（Ｂ５）脂肪族アルコールを変性したアクリル酸エステル（ｈ）等が挙げられる。 The compound having a (B) (meth) acrylate group of the present invention is not particularly limited. For example, at least the polymer polyol (a) having a hydroxyl group in the molecule and a (meth) having a substituent that reacts with a hydroxyl group. The compound obtained by making acrylate react is mentioned.
Specifically, (B1) a urethane (meta) obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule, a polyisocyanate (b), and a (meth) acrylate (c) having a hydroxyl group in the molecule. ) Acrylate (hereinafter referred to as urethane (meth) acrylate), (B2) a polymer obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule and (meth) acrylate (d) having an isocyanate group, And (B3) a polymer polyol obtained by a reaction of a polymer polyol (a) having a hydroxyl group in the molecule with an acrylate (e) having a carboxyl group such as acrylic acid.
In addition to the above, as the compound having (B) (meth) acrylate group of the present invention, (B4) a conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene and isoprene, After reacting the dibasic unsaturated acid anhydride (g), subsequently, (meth) acrylate having a hydroxyl group in the molecule in part or all of the acid anhydride residue in the obtained prepolymer Examples thereof include a conjugated diene polymer obtained by reacting (c), (B5) an acrylic ester (h) obtained by modifying an aliphatic alcohol, and the like.
具体的には、（Ｂ１）分子中にヒドロキシル基を有するポリマーポリオール（ａ）、ポリイソシアネート（ｂ）、及び分子中に水酸基を有する（メタ）アクリレート（ｃ）を反応させて得られるウレタン（メタ）アクリレート（以下、ウレタン（メタ）アクリレートという。）、（Ｂ２）分子中にヒドロキシル基を有するポリマーポリオール（ａ）、及びイソシアネート基を有する（メタ）アクリレート（ｄ）を反応させて得られる化合物、および（Ｂ３）分子中にヒドロキシル基を有するポリマーポリオール（ａ）とアクリル酸などのカルボキシル基を有するアクリレート（ｅ）との反応で得られるポリマーポリオール、等が挙げられる。
上記のほかに、本発明の（Ｂ）（メタ）アクリレート基を有する化合物としては、（Ｂ４）ブタジエン、イソプレンなどの共役ジエン化合物をアニオン重合して得られる共役ジエン系プレポリマー（ｆ）に、二塩基性不飽和酸無水物（ｇ）を反応させた後、引き続き、得られたプレポリマー中の酸無水物残基の一部、または、全部に、分子中に水酸基を有する（メタ）アクリレート（ｃ）を反応させることにより得られる共役ジエン系ポリマー、（Ｂ５）脂肪族アルコールを変性したアクリル酸エステル（ｈ）等が挙げられる。 The compound having a (B) (meth) acrylate group of the present invention is not particularly limited. For example, at least the polymer polyol (a) having a hydroxyl group in the molecule and a (meth) having a substituent that reacts with a hydroxyl group. The compound obtained by making acrylate react is mentioned.
Specifically, (B1) a urethane (meta) obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule, a polyisocyanate (b), and a (meth) acrylate (c) having a hydroxyl group in the molecule. ) Acrylate (hereinafter referred to as urethane (meth) acrylate), (B2) a polymer obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule and (meth) acrylate (d) having an isocyanate group, And (B3) a polymer polyol obtained by a reaction of a polymer polyol (a) having a hydroxyl group in the molecule with an acrylate (e) having a carboxyl group such as acrylic acid.
In addition to the above, as the compound having (B) (meth) acrylate group of the present invention, (B4) a conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene and isoprene, After reacting the dibasic unsaturated acid anhydride (g), subsequently, (meth) acrylate having a hydroxyl group in the molecule in part or all of the acid anhydride residue in the obtained prepolymer Examples thereof include a conjugated diene polymer obtained by reacting (c), (B5) an acrylic ester (h) obtained by modifying an aliphatic alcohol, and the like.
前記ヒドロキシル基を有するポリマーポリオール（ａ）は特に限定されないが具体的には、ポリエステルポリオール、ポリカーボネートポリオール、ポリエーテルポリオール、脂肪族炭化水素系ポリオール、脂環族炭化水素系ポリオールを使用することができる。
中でも、製造が簡便であり、種々の性能に優れることからポリエーテルポリオールが特に好ましい。 The polymer polyol (a) having a hydroxyl group is not particularly limited, and specifically, a polyester polyol, a polycarbonate polyol, a polyether polyol, an aliphatic hydrocarbon polyol, and an alicyclic hydrocarbon polyol can be used. .
Among these, polyether polyol is particularly preferable because it is easy to produce and excellent in various performances.
中でも、製造が簡便であり、種々の性能に優れることからポリエーテルポリオールが特に好ましい。 The polymer polyol (a) having a hydroxyl group is not particularly limited, and specifically, a polyester polyol, a polycarbonate polyol, a polyether polyol, an aliphatic hydrocarbon polyol, and an alicyclic hydrocarbon polyol can be used. .
Among these, polyether polyol is particularly preferable because it is easy to produce and excellent in various performances.
前記ポリエーテルポリオールは特に限定されないがポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、ポリテトラメチレングリコールを使用することができる。
硬化物の耐熱性、柔軟性および硬化型樹脂組成物の粘度の観点から、ポリエーテルポリオールの中で特にプロピレンオキサイドあるいはブチレンオキサイドあるいはテトラフルオロエチレンの開環重合により得られるポリエーテル鎖部分を含むポリエーテルポリオールが好ましい。 The polyether polyol is not particularly limited, and polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol can be used.
From the viewpoints of heat resistance of the cured product, flexibility and viscosity of the curable resin composition, among the polyether polyols, a poly-polyether containing a polyether chain portion obtained by ring-opening polymerization of propylene oxide, butylene oxide or tetrafluoroethylene is particularly preferred. Ether polyols are preferred.
硬化物の耐熱性、柔軟性および硬化型樹脂組成物の粘度の観点から、ポリエーテルポリオールの中で特にプロピレンオキサイドあるいはブチレンオキサイドあるいはテトラフルオロエチレンの開環重合により得られるポリエーテル鎖部分を含むポリエーテルポリオールが好ましい。 The polyether polyol is not particularly limited, and polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol can be used.
From the viewpoints of heat resistance of the cured product, flexibility and viscosity of the curable resin composition, among the polyether polyols, a poly-polyether containing a polyether chain portion obtained by ring-opening polymerization of propylene oxide, butylene oxide or tetrafluoroethylene is particularly preferred. Ether polyols are preferred.
前記ヒドロキシル基を有するポリマーポリオール（ａ）の数平均分子量は特に限定されないが５００以上２００００以下が好ましい。
５００未満であれば硬化物が硬くなりすぎ粘着剤としての柔軟性が失われ、２００００を超える場合は合成が困難となる。 The number average molecular weight of the polymer polyol (a) having a hydroxyl group is not particularly limited, but is preferably 500 or more and 20000 or less.
If it is less than 500, hardened | cured material will become hard too much and the softness | flexibility as an adhesive will be lost, and a synthesis | combination will become difficult when it exceeds 20000.
５００未満であれば硬化物が硬くなりすぎ粘着剤としての柔軟性が失われ、２００００を超える場合は合成が困難となる。 The number average molecular weight of the polymer polyol (a) having a hydroxyl group is not particularly limited, but is preferably 500 or more and 20000 or less.
If it is less than 500, hardened | cured material will become hard too much and the softness | flexibility as an adhesive will be lost, and a synthesis | combination will become difficult when it exceeds 20000.
前記ポリイソシアネート（ｂ）は特に限定されないが具体的には、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネートを挙げることができる。
脂肪族ポリイソシアネートとしては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、３－メチルペンタン－１，５－ジイソシアネート等を挙げることができる。
脂環族ポリイソシアネートとしては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン等を挙げることができる。芳香族ポリイソシアネートとしては、トリレンジイソシアネート、２，２’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、４，４’－ジベンジルジイソシアネート、１，５－ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート等を挙げることができる。
芳香脂肪族ポリイソシアネートとしては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α´，α´－テトラメチルキシリレンジイソシアネート等を挙げることができる。また、これらの有機ポリイソシアネートの２量体、３量体やビュレット化イソシアネート等の変性体を挙げることができる。これらは、単独で又は２種以上を併用して用いることもできる。
低粘度化への観点からはヘキサメチレンジイソシアネートが好ましく、耐熱黄変性の観点からは、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネートを使用することが好ましい。 The polyisocyanate (b) is not particularly limited, and specific examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.
Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 , 5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like.
Examples of alicyclic polyisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Can be mentioned. Aromatic polyisocyanates include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5 -Naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.
Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like. Moreover, modified bodies, such as a dimer, a trimer of these organic polyisocyanate, and a buret-ized isocyanate, can be mentioned. These may be used alone or in combination of two or more.
Hexamethylene diisocyanate is preferable from the viewpoint of lowering the viscosity, and isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate should be used from the viewpoint of heat-resistant yellowing. Is preferred.
脂肪族ポリイソシアネートとしては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、３－メチルペンタン－１，５－ジイソシアネート等を挙げることができる。
脂環族ポリイソシアネートとしては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン等を挙げることができる。芳香族ポリイソシアネートとしては、トリレンジイソシアネート、２，２’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、４，４’－ジベンジルジイソシアネート、１，５－ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート等を挙げることができる。
芳香脂肪族ポリイソシアネートとしては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α´，α´－テトラメチルキシリレンジイソシアネート等を挙げることができる。また、これらの有機ポリイソシアネートの２量体、３量体やビュレット化イソシアネート等の変性体を挙げることができる。これらは、単独で又は２種以上を併用して用いることもできる。
低粘度化への観点からはヘキサメチレンジイソシアネートが好ましく、耐熱黄変性の観点からは、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネートを使用することが好ましい。 The polyisocyanate (b) is not particularly limited, and specific examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.
Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 , 5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like.
Examples of alicyclic polyisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Can be mentioned. Aromatic polyisocyanates include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5 -Naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.
Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like. Moreover, modified bodies, such as a dimer, a trimer of these organic polyisocyanate, and a buret-ized isocyanate, can be mentioned. These may be used alone or in combination of two or more.
Hexamethylene diisocyanate is preferable from the viewpoint of lowering the viscosity, and isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate should be used from the viewpoint of heat-resistant yellowing. Is preferred.
前記分子中に水酸基を有する（メタ）アクリレート（ｃ）は、特に限定されないが具体的には、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルアクリレート、カプロラクトン変性－２－ヒドロキシエチルアクリレート、ポリエチレングリコールモノ（メタ）アクリル酸エステル、ポリプロピレグリコールモノアクリル酸エステル、ポリブチレングリコールモノ（メタ）アクリル酸エステル、２-（メタ）アクリロイロキシエチル-２-ヒドロキシエチルフタレート、フェニルグリシジルエーテル（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられ、これらを単独使用または複数種併用することができる。
この中でも低粘度化への観点から、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、カプロラクトン変性－２－ヒドロキシエチルアクリレート、ポリエチレングリコールモノ（メタ）アクリル酸エステル、ポリプロピレグリコールモノアクリル酸エステルを使用することが好ましい。 The (meth) acrylate (c) having a hydroxyl group in the molecule is not particularly limited. Specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4 -Hydroxybutyl acrylate, caprolactone-modified-2-hydroxyethyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol monoacrylate, polybutylene glycol mono (meth) acrylate, 2- (meth) acryloyloxy Ethyl-2-hydroxyethyl phthalate, phenyl glycidyl ether (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, potassium Rorakuton modified dipentaerythritol penta (meth) acrylate and the like, can be used in combination singly used or more.
Among these, from the viewpoint of lowering the viscosity, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, caprolactone-modified-2-hydroxyethyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono Preference is given to using acrylic esters.
この中でも低粘度化への観点から、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、カプロラクトン変性－２－ヒドロキシエチルアクリレート、ポリエチレングリコールモノ（メタ）アクリル酸エステル、ポリプロピレグリコールモノアクリル酸エステルを使用することが好ましい。 The (meth) acrylate (c) having a hydroxyl group in the molecule is not particularly limited. Specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4 -Hydroxybutyl acrylate, caprolactone-modified-2-hydroxyethyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol monoacrylate, polybutylene glycol mono (meth) acrylate, 2- (meth) acryloyloxy Ethyl-2-hydroxyethyl phthalate, phenyl glycidyl ether (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, potassium Rorakuton modified dipentaerythritol penta (meth) acrylate and the like, can be used in combination singly used or more.
Among these, from the viewpoint of lowering the viscosity, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, caprolactone-modified-2-hydroxyethyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono Preference is given to using acrylic esters.
前記イソシアナート基を有する（メタ）アクリレート（ｄ）は、特に限定されないが具体的には２－アクリロイルオキシエチルイソシアナート、２－メタクリロイルオキシエチルイソシアナートが挙げられる。これらは単独で使用することも複数併用することもできる。
The (meth) acrylate (d) having an isocyanate group is not particularly limited, and specific examples include 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate. These can be used alone or in combination.
前記アクリル酸などのカルボキシル基を有するアクリレート（ｅ）は、特に限定されないが具体的には２－アクリロイロキシエチルコハク酸、２－アクリロイロキシエチルフタル酸、２－アクリロイロキシエチルヘキサヒドロフタル酸、アクリル酸等が挙げられる。
これらは単独で使用することも複数併用することもできる。 The acrylate (e) having a carboxyl group such as acrylic acid is not particularly limited. Specifically, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthal An acid, acrylic acid, etc. are mentioned.
These can be used alone or in combination.
これらは単独で使用することも複数併用することもできる。 The acrylate (e) having a carboxyl group such as acrylic acid is not particularly limited. Specifically, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthal An acid, acrylic acid, etc. are mentioned.
These can be used alone or in combination.
前記ブタジエン、イソプレンなどの共役ジエン化合物をアニオン重合して得られる共役ジエン系プレポリマー（ｆ）は、例えばブタジエン、イソプレン、１，３－ペンタジエン、２，３－ジメチルブタジエン、１－フェニルブタジエン、２－フェニルブタジエン、１，１－ジフェニルブタジエン、１，２－ジフェニルブタジエン、２，３－ジフェニルブタジエンなどが挙げられる。
共役ジエン系ポリマーはこれらの共役ジエン化合物の１種類単独で構成されていてもよく、２種類以上から構成されていてもよい。
共役ジエン系プレポリマーとしては、ポリブタジエン、ポリイソプレン、またはイソプレンとブタジエンの混合物の共重合体などが特に好ましい。
共役ジエン系プレポリマーは、ブタジエン、イソプレンなどの上記した共役ジエン化合物を、ナトリウムナフタレン錯体、ｎ－ブチルリチウム、ｓ－ブチルリチウム、メチルリチウム、エチルリチウム、ペンチルリチウムなどのアルキルリチウムなどを開始剤としてアニオン重合させることにより製造することもできるし、アゾビスイソブチロニトリルなどのアゾビスニトリル化合物、ベンゾイルパーオキサイドなどの過酸化物を開始剤としてラジカル重合させることによっても製造することができる。
なお、これらの重合反応は、通常、ヘキサン、ヘプタン、トルエン、キシレンなどの脂肪族または芳香族炭化水素系溶媒の存在下に、重合温度－８０℃～１５０℃、重合時間１～１００時間という条件で行うことができる。
前記化合物の数平均分子量は特に限定されないが５００以上８００００以下が好ましい。
５００未満は合成が困難であり、８００００を超える場合は高粘度化し使用するのが難しくなる。 The conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene is, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenylbutadiene, 2 -Phenylbutadiene, 1,1-diphenylbutadiene, 1,2-diphenylbutadiene, 2,3-diphenylbutadiene and the like.
The conjugated diene polymer may be composed of one kind of these conjugated diene compounds or may be composed of two or more kinds.
As the conjugated diene prepolymer, polybutadiene, polyisoprene, or a copolymer of a mixture of isoprene and butadiene is particularly preferable.
Conjugated diene prepolymers are prepared by using the above conjugated diene compounds such as butadiene and isoprene as initiators such as sodium naphthalene complex, n-butyllithium, s-butyllithium, methyllithium, ethyllithium, and alkyllithium such as pentyllithium. It can also be produced by anionic polymerization, or by radical polymerization using an azobisnitrile compound such as azobisisobutyronitrile and a peroxide such as benzoyl peroxide as an initiator.
These polymerization reactions are usually performed under the conditions of a polymerization temperature of −80 ° C. to 150 ° C. and a polymerization time of 1 to 100 hours in the presence of an aliphatic or aromatic hydrocarbon solvent such as hexane, heptane, toluene, and xylene. Can be done.
The number average molecular weight of the compound is not particularly limited, but is preferably 500 or more and 80000 or less.
If it is less than 500, the synthesis is difficult, and if it exceeds 80000, the viscosity becomes high and it becomes difficult to use.
共役ジエン系ポリマーはこれらの共役ジエン化合物の１種類単独で構成されていてもよく、２種類以上から構成されていてもよい。
共役ジエン系プレポリマーとしては、ポリブタジエン、ポリイソプレン、またはイソプレンとブタジエンの混合物の共重合体などが特に好ましい。
共役ジエン系プレポリマーは、ブタジエン、イソプレンなどの上記した共役ジエン化合物を、ナトリウムナフタレン錯体、ｎ－ブチルリチウム、ｓ－ブチルリチウム、メチルリチウム、エチルリチウム、ペンチルリチウムなどのアルキルリチウムなどを開始剤としてアニオン重合させることにより製造することもできるし、アゾビスイソブチロニトリルなどのアゾビスニトリル化合物、ベンゾイルパーオキサイドなどの過酸化物を開始剤としてラジカル重合させることによっても製造することができる。
なお、これらの重合反応は、通常、ヘキサン、ヘプタン、トルエン、キシレンなどの脂肪族または芳香族炭化水素系溶媒の存在下に、重合温度－８０℃～１５０℃、重合時間１～１００時間という条件で行うことができる。
前記化合物の数平均分子量は特に限定されないが５００以上８００００以下が好ましい。
５００未満は合成が困難であり、８００００を超える場合は高粘度化し使用するのが難しくなる。 The conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene is, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenylbutadiene, 2 -Phenylbutadiene, 1,1-diphenylbutadiene, 1,2-diphenylbutadiene, 2,3-diphenylbutadiene and the like.
The conjugated diene polymer may be composed of one kind of these conjugated diene compounds or may be composed of two or more kinds.
As the conjugated diene prepolymer, polybutadiene, polyisoprene, or a copolymer of a mixture of isoprene and butadiene is particularly preferable.
Conjugated diene prepolymers are prepared by using the above conjugated diene compounds such as butadiene and isoprene as initiators such as sodium naphthalene complex, n-butyllithium, s-butyllithium, methyllithium, ethyllithium, and alkyllithium such as pentyllithium. It can also be produced by anionic polymerization, or by radical polymerization using an azobisnitrile compound such as azobisisobutyronitrile and a peroxide such as benzoyl peroxide as an initiator.
These polymerization reactions are usually performed under the conditions of a polymerization temperature of −80 ° C. to 150 ° C. and a polymerization time of 1 to 100 hours in the presence of an aliphatic or aromatic hydrocarbon solvent such as hexane, heptane, toluene, and xylene. Can be done.
The number average molecular weight of the compound is not particularly limited, but is preferably 500 or more and 80000 or less.
If it is less than 500, the synthesis is difficult, and if it exceeds 80000, the viscosity becomes high and it becomes difficult to use.
前記二塩基性不飽和酸無水物（ｇ）は、特に限定されないが具体的には無水フタル酸、無水フタル酸、無水ピロメリット酸、無水テトラカルボン酸等が挙げられる。これらは単独で使用することも複数併用することもできる。
The dibasic unsaturated acid anhydride (g) is not particularly limited, and specific examples include phthalic anhydride, phthalic anhydride, pyromellitic anhydride, and tetracarboxylic anhydride. These can be used alone or in combination.
前記脂肪族アルコールを変性したアクリル酸エステル（ｈ）としては、特に限定されないが具体的には、３,３,５－トリメチルシクロヘキサン（メタ）アクリレート、２－（２－エトキシエトキシ）エチル（メタ）アクリレート、環状トリメチロールプロパンホルマール（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、イソトリデシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソボロニル（メタ）アクリレート、イソノニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メトキシトリエチレングリコールアクリレート、メトキシポリエチレングリコール（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート、シクロヘキサンスピロ－２－（１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート、３－エチル－３－オキセタニルメチルアクリレート、アダマンチル（メタ）アクリレート、１，６－ヘキサンジオールジアクリレート、１，９－ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ジオキサングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、等が挙げられる。これらは単独で用いても、複数種を併用してもよい。
特に、低粘度および低臭気性の観点からラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレートが好ましい。 The acrylic ester (h) obtained by modifying the aliphatic alcohol is not particularly limited, but specific examples include 3,3,5-trimethylcyclohexane (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth). Acrylate, cyclic trimethylolpropane formal (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, isotridecyl (meth) acrylate, octyl (meth) acrylate, isobornyl (Meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol (meth) acrylate, (2-me 2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl (meth) acrylate, 3-ethyl-3- Oxetanyl methyl acrylate, adamantyl (meth) acrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, And dipropylene glycol di (meth) acrylate. These may be used alone or in combination.
In particular, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and 1,9-nonanediol di (meth) acrylate are preferable from the viewpoint of low viscosity and low odor.
特に、低粘度および低臭気性の観点からラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレートが好ましい。 The acrylic ester (h) obtained by modifying the aliphatic alcohol is not particularly limited, but specific examples include 3,3,5-trimethylcyclohexane (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth). Acrylate, cyclic trimethylolpropane formal (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, isotridecyl (meth) acrylate, octyl (meth) acrylate, isobornyl (Meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol (meth) acrylate, (2-me 2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl (meth) acrylate, 3-ethyl-3- Oxetanyl methyl acrylate, adamantyl (meth) acrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, And dipropylene glycol di (meth) acrylate. These may be used alone or in combination.
In particular, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and 1,9-nonanediol di (meth) acrylate are preferable from the viewpoint of low viscosity and low odor.
前記ウレタン（メタ）アクリレート（Ｂ１）は、公知の方法で合成することが可能である。
例えば、所定量の（ｂ）成分を過剰量の（ａ）成分に投入し、８０℃で所定の遊離イソシアネート量になるまで反応させることでポリウレタンを得て、更に７０～８０℃でさらにハイドロキノンモノメチルエーテル等の重合禁止剤の存在下、（ｃ）成分を一括で仕込み、７０～８０℃で遊離イソシアネートが無くなるまで加温・攪拌することで合成可能である。
この時、反応を促進させるために、ジブチルチンジラウレート等のスズ系触媒を添加することもできる。 The urethane (meth) acrylate (B1) can be synthesized by a known method.
For example, a predetermined amount of component (b) is added to an excessive amount of component (a) and reacted at 80 ° C. until a predetermined amount of free isocyanate is obtained to obtain polyurethane, and further at 70-80 ° C., further hydroquinone monomethyl In the presence of a polymerization inhibitor such as ether, the component (c) can be charged all at once and heated and stirred at 70 to 80 ° C. until free isocyanate disappears.
At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.
例えば、所定量の（ｂ）成分を過剰量の（ａ）成分に投入し、８０℃で所定の遊離イソシアネート量になるまで反応させることでポリウレタンを得て、更に７０～８０℃でさらにハイドロキノンモノメチルエーテル等の重合禁止剤の存在下、（ｃ）成分を一括で仕込み、７０～８０℃で遊離イソシアネートが無くなるまで加温・攪拌することで合成可能である。
この時、反応を促進させるために、ジブチルチンジラウレート等のスズ系触媒を添加することもできる。 The urethane (meth) acrylate (B1) can be synthesized by a known method.
For example, a predetermined amount of component (b) is added to an excessive amount of component (a) and reacted at 80 ° C. until a predetermined amount of free isocyanate is obtained to obtain polyurethane, and further at 70-80 ° C., further hydroquinone monomethyl In the presence of a polymerization inhibitor such as ether, the component (c) can be charged all at once and heated and stirred at 70 to 80 ° C. until free isocyanate disappears.
At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.
前記ウレタン（メタ）アクリレート（Ｂ１）において、（ａ）と（ｂ）を反応させて得られるポリウレタンの官能基数が１．０以上、４．０以下である。
官能基数が１．０未満の場合は硬化物が流動性をもち経時的に流れ出す恐れがあり、４.０を超える場合は硬化物が硬くなりすぎる。
また、前記（ｃ）の割合は（ｂ）-（ａ）に対し１.０～２．０モル比であるが、１．０～１．５モル比が好ましい。 In the urethane (meth) acrylate (B1), the number of functional groups of polyurethane obtained by reacting (a) and (b) is 1.0 or more and 4.0 or less.
When the number of functional groups is less than 1.0, the cured product has fluidity and may flow out with time, and when it exceeds 4.0, the cured product becomes too hard.
The ratio of (c) is 1.0 to 2.0 molar ratio with respect to (b)-(a), but 1.0 to 1.5 molar ratio is preferable.
官能基数が１．０未満の場合は硬化物が流動性をもち経時的に流れ出す恐れがあり、４.０を超える場合は硬化物が硬くなりすぎる。
また、前記（ｃ）の割合は（ｂ）-（ａ）に対し１.０～２．０モル比であるが、１．０～１．５モル比が好ましい。 In the urethane (meth) acrylate (B1), the number of functional groups of polyurethane obtained by reacting (a) and (b) is 1.0 or more and 4.0 or less.
When the number of functional groups is less than 1.0, the cured product has fluidity and may flow out with time, and when it exceeds 4.0, the cured product becomes too hard.
The ratio of (c) is 1.0 to 2.0 molar ratio with respect to (b)-(a), but 1.0 to 1.5 molar ratio is preferable.
前記（Ｂ２）分子中にヒドロキシル基を有するポリマーポリオール（ａ）、及びイソシアネート基を有する（メタ）アクリレート（ｄ）を反応させて得られる化合物は、公知の方法で合成することが可能である。
例えば、所定量の（ａ）成分を投入し、（d）成分を一括で仕込み、７０～８０℃で遊離イソシアネートが無くなるまで加温・攪拌することで合成可能である。この時、反応を促進させるために、ジブチルチンジラウレート等のスズ系触媒を添加することもできる。 The compound obtained by reacting the polymer polyol (a) having a hydroxyl group in the molecule (B2) and the (meth) acrylate (d) having an isocyanate group can be synthesized by a known method.
For example, it can be synthesized by charging a predetermined amount of the component (a), charging the component (d) all together, and heating and stirring at 70 to 80 ° C. until free isocyanate is eliminated. At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.
例えば、所定量の（ａ）成分を投入し、（d）成分を一括で仕込み、７０～８０℃で遊離イソシアネートが無くなるまで加温・攪拌することで合成可能である。この時、反応を促進させるために、ジブチルチンジラウレート等のスズ系触媒を添加することもできる。 The compound obtained by reacting the polymer polyol (a) having a hydroxyl group in the molecule (B2) and the (meth) acrylate (d) having an isocyanate group can be synthesized by a known method.
For example, it can be synthesized by charging a predetermined amount of the component (a), charging the component (d) all together, and heating and stirring at 70 to 80 ° C. until free isocyanate is eliminated. At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.
前記（Ｂ３）分子中にヒドロキシル基を有するポリマーポリオール（ａ）とアクリル酸などのカルボキシル基を有するアクリレート（ｅ）との反応で得られるポリマーポリオールとしは、公知の方法で合成することが可能である。
例えば、所定量の（ａ）成分を投入し、過剰量の（ｅ）を投入し、パラトルエンスルホン酸などの触媒を用いて脱水エステル化反応することにより得られる。
このとき、通常、ベンゼン、トルエン、シクロヘキサンなどの脂肪族または芳香族炭化水素系溶媒の存在下に、脱水エステル化温度７０℃～１５０℃、反応時間１～２０時間という条件で行うことができる。 The polymer polyol obtained by the reaction of the polymer polyol (a) having a hydroxyl group in the molecule (B3) and the acrylate (e) having a carboxyl group such as acrylic acid can be synthesized by a known method. is there.
For example, it can be obtained by adding a predetermined amount of component (a), adding an excessive amount of (e), and performing a dehydration esterification reaction using a catalyst such as paratoluenesulfonic acid.
In this case, the reaction can be usually carried out in the presence of an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene, cyclohexane and the like, under conditions of a dehydration esterification temperature of 70 ° C. to 150 ° C. and a reaction time of 1 to 20 hours.
例えば、所定量の（ａ）成分を投入し、過剰量の（ｅ）を投入し、パラトルエンスルホン酸などの触媒を用いて脱水エステル化反応することにより得られる。
このとき、通常、ベンゼン、トルエン、シクロヘキサンなどの脂肪族または芳香族炭化水素系溶媒の存在下に、脱水エステル化温度７０℃～１５０℃、反応時間１～２０時間という条件で行うことができる。 The polymer polyol obtained by the reaction of the polymer polyol (a) having a hydroxyl group in the molecule (B3) and the acrylate (e) having a carboxyl group such as acrylic acid can be synthesized by a known method. is there.
For example, it can be obtained by adding a predetermined amount of component (a), adding an excessive amount of (e), and performing a dehydration esterification reaction using a catalyst such as paratoluenesulfonic acid.
In this case, the reaction can be usually carried out in the presence of an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene, cyclohexane and the like, under conditions of a dehydration esterification temperature of 70 ° C. to 150 ° C. and a reaction time of 1 to 20 hours.
前記（Ｂ４）ブタジエン、イソプレンなどの共役ジエン化合物をアニオン重合して得られる共役ジエン系プレポリマー（ｆ）に、二塩基性不飽和酸無水物（ｇ）を反応させた後、引き続き、得られたプレポリマー中の酸無水物残基の一部、または、全部に、分子中に水酸基を有する（メタ）アクリレート（ｃ）を反応させることにより得られる共役ジエン系ポリマーとしては、市販品のものを用いることができる。
例えば、クラレ社製 商品名：クラプレンＵＣ－１０２、ＵＣ－２０３等を挙げることができる。
本発明の（Ｂ）（メタ）アクリレート基を有する化合物の含有量は、当該硬化型樹脂組成物の１００質量％に対して、１質量％以上９９質量％以下が好ましく、より好ましくは１０質量％以上９８質量％以下で、更に好ましくは、２０質量％以上９７質量％以下である。
１質量％未満の場合では、硬化性が悪くなる恐れがあり、９９質量％超の場合は、耐熱試験後に黄変する恐れがある。 (B4) A conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene is reacted with a dibasic unsaturated acid anhydride (g) and then obtained. The conjugated diene polymer obtained by reacting a part or all of the acid anhydride residue in the prepolymer with a (meth) acrylate (c) having a hydroxyl group in the molecule is a commercially available product. Can be used.
For example, trade names manufactured by Kuraray Co., Ltd .: Claprene UC-102, UC-203, and the like can be mentioned.
The content of the compound having a (B) (meth) acrylate group of the present invention is preferably 1% by mass or more and 99% by mass or less, more preferably 10% by mass with respect to 100% by mass of the curable resin composition. It is 98 mass% or less, More preferably, it is 20 mass% or more and 97 mass% or less.
If it is less than 1% by mass, the curability may be deteriorated. If it exceeds 99% by mass, it may be yellowed after the heat resistance test.
例えば、クラレ社製 商品名：クラプレンＵＣ－１０２、ＵＣ－２０３等を挙げることができる。
本発明の（Ｂ）（メタ）アクリレート基を有する化合物の含有量は、当該硬化型樹脂組成物の１００質量％に対して、１質量％以上９９質量％以下が好ましく、より好ましくは１０質量％以上９８質量％以下で、更に好ましくは、２０質量％以上９７質量％以下である。
１質量％未満の場合では、硬化性が悪くなる恐れがあり、９９質量％超の場合は、耐熱試験後に黄変する恐れがある。 (B4) A conjugated diene prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene is reacted with a dibasic unsaturated acid anhydride (g) and then obtained. The conjugated diene polymer obtained by reacting a part or all of the acid anhydride residue in the prepolymer with a (meth) acrylate (c) having a hydroxyl group in the molecule is a commercially available product. Can be used.
For example, trade names manufactured by Kuraray Co., Ltd .: Claprene UC-102, UC-203, and the like can be mentioned.
The content of the compound having a (B) (meth) acrylate group of the present invention is preferably 1% by mass or more and 99% by mass or less, more preferably 10% by mass with respect to 100% by mass of the curable resin composition. It is 98 mass% or less, More preferably, it is 20 mass% or more and 97 mass% or less.
If it is less than 1% by mass, the curability may be deteriorated. If it exceeds 99% by mass, it may be yellowed after the heat resistance test.
本発明の硬化性樹脂組成物は必要に応じ活性エネルギー線による重合開始剤を添加する。
ここでいう活性エネルギー線による重合開始剤は、光重合開始剤と紫外線等の活性エネルギー線による重合開始剤との双方を含むものとする。 The curable resin composition of this invention adds the polymerization initiator by an active energy ray as needed.
The polymerization initiator by active energy rays here includes both a photopolymerization initiator and a polymerization initiator by active energy rays such as ultraviolet rays.
ここでいう活性エネルギー線による重合開始剤は、光重合開始剤と紫外線等の活性エネルギー線による重合開始剤との双方を含むものとする。 The curable resin composition of this invention adds the polymerization initiator by an active energy ray as needed.
The polymerization initiator by active energy rays here includes both a photopolymerization initiator and a polymerization initiator by active energy rays such as ultraviolet rays.
光重合開始剤としては、たとえば、ベンゾフェノン等の芳香族ケトン類、アントラセン、α－クロロメチルナフタレン等の芳香族化合物、ジフェニルスルフィド、チオカーバメイト等のイオウ化合物を使用することができる。
可視光以外の紫外線などの活性エネルギー線による重合開始剤としては、例えば、アセトフェノン、アセトフェノンベンジルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、キサントン、フルオレノン、ベンズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、３－メチルアセトフェノン、４－クロロベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４，４’－ジアミノベンゾフェノン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、チオキサントン、ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパン－１－オン、２－ベンジルー２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１，４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキシド、オリゴ（２－ヒドロキシ－２－メチル－１－（４－（１－メチルビニル）フェニル）プロパノン）、オキシフェニル酢酸、2-[2-オキソ-2-フェニルアセトキシエトキシ]エチルエステルとオキシフェニル酢酸，2-(2-ヒドロキシエトキシ)エチルエステルの混合物等を挙げることができる。 As the photopolymerization initiator, for example, aromatic ketones such as benzophenone, aromatic compounds such as anthracene and α-chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate can be used.
Examples of polymerization initiators using active energy rays such as ultraviolet rays other than visible light include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and xanthone. , Fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one Thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), oxyphenylacetic acid, 2 -[2-oxo-2-phenylacetoxyethoxy] ethyl ester and Examples thereof include a mixture of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester.
可視光以外の紫外線などの活性エネルギー線による重合開始剤としては、例えば、アセトフェノン、アセトフェノンベンジルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、キサントン、フルオレノン、ベンズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、３－メチルアセトフェノン、４－クロロベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４，４’－ジアミノベンゾフェノン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、チオキサントン、ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパン－１－オン、２－ベンジルー２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１，４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキシド、オリゴ（２－ヒドロキシ－２－メチル－１－（４－（１－メチルビニル）フェニル）プロパノン）、オキシフェニル酢酸、2-[2-オキソ-2-フェニルアセトキシエトキシ]エチルエステルとオキシフェニル酢酸，2-(2-ヒドロキシエトキシ)エチルエステルの混合物等を挙げることができる。 As the photopolymerization initiator, for example, aromatic ketones such as benzophenone, aromatic compounds such as anthracene and α-chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate can be used.
Examples of polymerization initiators using active energy rays such as ultraviolet rays other than visible light include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and xanthone. , Fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one Thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), oxyphenylacetic acid, 2 -[2-oxo-2-phenylacetoxyethoxy] ethyl ester and Examples thereof include a mixture of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester.
活性エネルギー線による重合開始剤の市販品としては、例えば、ＢＡＳＦ社製 商品名：イルガキュア１８４，３６９，６５１，５００，７５４，８１９，９０７，７８４，２９５９，１０００，１３００，１７００，１８００，１８５０、ダロキュア１１１６，１１７３、ルシリンＴＰＯ、ＵＣＢ社製 商品名：ユベクリルＰ３６、フラテツリ・ランベルティ社製 商品名：エザキュアーＫＩＰ１５０，ＫＩＰ１００Ｆ，ＫＴ３７，ＫＴ５５，ＫＴＯ４６，ＴＺＴ，ＫＩＰ７５ＬＴ、日本化薬社製 商品名：カヤキュアＤＥＴＸ等を挙げることができる。
As a commercial item of the polymerization initiator by an active energy ray, for example, the product name: Irgacure 184,369,651,500,754,819,907,784,2959,1000,1300,1700,1800,1850 made by BASF Darocur 1116, 1173, Lucyrin TPO, manufactured by UCB Co., Ltd. Product name: Ubekrill P36, Fratteri Lamberti Co., Ltd. Product name: Ezacure KIP150, KIP100F, KT37, KT55, KTO46, TZT, KIP75LT, Nihon Kayaku Co., Ltd. Product name: Kayacure DETX etc. can be mentioned.
これら重合開始剤の含有量はその種類等によって異なるが、目安としては硬化型樹脂組成物１００質量部に対して１～８質量部である。含有量が少なすぎると活性エネルギー線感度が不十分となり、多すぎると硬化物深部まで活性エネルギー線が十分に届かず、硬化物深部の硬化性が低下する傾向がある。
なお、本発明の硬化性樹脂組成物を硬化させるエネルギー線源は特に限定されないが、例としては、高圧水銀灯、電子線、γ線、カーボンアーク灯、キセノン灯、メタルハライド灯等が挙げられる。
一方、加熱によって硬化させる場合は、６０～２５０℃の温度領域に加熱することによって硬化させることができる。 The content of these polymerization initiators varies depending on the type and the like, but as a guide, it is 1 to 8 parts by mass with respect to 100 parts by mass of the curable resin composition. When the content is too small, the active energy ray sensitivity becomes insufficient, and when it is too much, the active energy ray does not reach the depth of the cured product sufficiently, and the curability of the cured product deep portion tends to decrease.
The energy ray source for curing the curable resin composition of the present invention is not particularly limited, and examples thereof include a high pressure mercury lamp, an electron beam, a γ ray, a carbon arc lamp, a xenon lamp, and a metal halide lamp.
On the other hand, when cured by heating, it can be cured by heating to a temperature range of 60 to 250 ° C.
なお、本発明の硬化性樹脂組成物を硬化させるエネルギー線源は特に限定されないが、例としては、高圧水銀灯、電子線、γ線、カーボンアーク灯、キセノン灯、メタルハライド灯等が挙げられる。
一方、加熱によって硬化させる場合は、６０～２５０℃の温度領域に加熱することによって硬化させることができる。 The content of these polymerization initiators varies depending on the type and the like, but as a guide, it is 1 to 8 parts by mass with respect to 100 parts by mass of the curable resin composition. When the content is too small, the active energy ray sensitivity becomes insufficient, and when it is too much, the active energy ray does not reach the depth of the cured product sufficiently, and the curability of the cured product deep portion tends to decrease.
The energy ray source for curing the curable resin composition of the present invention is not particularly limited, and examples thereof include a high pressure mercury lamp, an electron beam, a γ ray, a carbon arc lamp, a xenon lamp, and a metal halide lamp.
On the other hand, when cured by heating, it can be cured by heating to a temperature range of 60 to 250 ° C.
本発明の硬化性樹脂組成物には、前記有機溶剤又はモノマー類、各種開始剤以外に、塗料、コーティング剤等に通常含まれる各種添加剤を必要に応じて添加することができる。
添加剤の例としては、光安定剤、紫外線吸収剤、触媒、消泡剤、重合促進剤、酸化防止剤、難燃剤、赤外線吸収剤、帯電防止剤、可塑剤、分散剤等が挙げられる。 In addition to the organic solvent or monomers and various initiators, various additives usually contained in paints, coating agents, and the like can be added to the curable resin composition of the present invention as necessary.
Examples of the additive include a light stabilizer, an ultraviolet absorber, a catalyst, an antifoaming agent, a polymerization accelerator, an antioxidant, a flame retardant, an infrared absorber, an antistatic agent, a plasticizer, and a dispersant.
添加剤の例としては、光安定剤、紫外線吸収剤、触媒、消泡剤、重合促進剤、酸化防止剤、難燃剤、赤外線吸収剤、帯電防止剤、可塑剤、分散剤等が挙げられる。 In addition to the organic solvent or monomers and various initiators, various additives usually contained in paints, coating agents, and the like can be added to the curable resin composition of the present invention as necessary.
Examples of the additive include a light stabilizer, an ultraviolet absorber, a catalyst, an antifoaming agent, a polymerization accelerator, an antioxidant, a flame retardant, an infrared absorber, an antistatic agent, a plasticizer, and a dispersant.
以上詳述した本発明の硬化性樹脂組成物は、粘着性、耐熱黄変性といった性能を有することから、携帯電話、電子書籍、タッチパネル等の電子端末や液晶テレビ、プラズマテレビ、有機ＥＬテレビ等の表示装置の表示パネルと保護板との間の空間の充填剤として用いることができる。
Since the curable resin composition of the present invention described in detail above has performance such as adhesiveness and heat-resistant yellowing, it can be used for electronic terminals such as mobile phones, electronic books, touch panels, liquid crystal televisions, plasma televisions, organic EL televisions, etc. It can be used as a filler for the space between the display panel of the display device and the protective plate.
本発明について、実施例に基づいてより具体的に説明するが、本発明はこれに限定されるものではない。当業者は本発明の範囲を逸脱することなく、種々の変更、修正、および改変を行うことができる。
The present invention will be described more specifically based on examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.
（ウレタンアクリレートの合成例）
［合成例１］
フラスコにトリレンジイソシアネート３４８ｇ（２モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが１００００であるポリプロピレングリコール（旭硝子社製、品番プレミノールＳ４０１１）１００００ｇ（１モル）を仕込み、８０℃にて遊離イソシアネートが０．８１％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル５．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－１を得た。 (Synthesis example of urethane acrylate)
[Synthesis Example 1]
A flask is charged with 348 g (2 mol) of tolylene diisocyanate and 10000 g (1 mol) of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., product number Preminol S4011) having a number average molecular weight Mn of 10,000 as a polyether polyol. The polyurethane was synthesized by reacting until it reached 81%.
The obtained polyurethane was charged with 5.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116), and reacted at 70 to 80 ° C. until the free isocyanate content became 0.1% or less. As a result, urethane acrylate B-1 was obtained.
［合成例１］
フラスコにトリレンジイソシアネート３４８ｇ（２モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが１００００であるポリプロピレングリコール（旭硝子社製、品番プレミノールＳ４０１１）１００００ｇ（１モル）を仕込み、８０℃にて遊離イソシアネートが０．８１％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル５．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－１を得た。 (Synthesis example of urethane acrylate)
[Synthesis Example 1]
A flask is charged with 348 g (2 mol) of tolylene diisocyanate and 10000 g (1 mol) of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., product number Preminol S4011) having a number average molecular weight Mn of 10,000 as a polyether polyol. The polyurethane was synthesized by reacting until it reached 81%.
The obtained polyurethane was charged with 5.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116), and reacted at 70 to 80 ° C. until the free isocyanate content became 0.1% or less. As a result, urethane acrylate B-1 was obtained.
［合成例２］
フラスコにイソホロンジイソシアネート６６６ｇ（３モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが３０００であるポリブチレングリコール（第一工業製薬社製、品番ＰＢＧ－３０００）６０００ｇ（２モル）を仕込み、８０℃にて遊離イソシアネートが１．２６％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル３．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－２を得た。 [Synthesis Example 2]
The flask was charged with 666 g (3 mol) of isophorone diisocyanate and 6000 g (2 mol) of polybutylene glycol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product number PBG-3000) having a number average molecular weight Mn of 3000 as a polyether polyol. Polyurethane was synthesized by reacting until the free isocyanate was 1.26%.
The obtained polyurethane was charged with 3.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) and allowed to react at 70 to 80 ° C. until the amount of free isocyanate was 0.1% or less. As a result, urethane acrylate B-2 was obtained.
フラスコにイソホロンジイソシアネート６６６ｇ（３モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが３０００であるポリブチレングリコール（第一工業製薬社製、品番ＰＢＧ－３０００）６０００ｇ（２モル）を仕込み、８０℃にて遊離イソシアネートが１．２６％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル３．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－２を得た。 [Synthesis Example 2]
The flask was charged with 666 g (3 mol) of isophorone diisocyanate and 6000 g (2 mol) of polybutylene glycol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product number PBG-3000) having a number average molecular weight Mn of 3000 as a polyether polyol. Polyurethane was synthesized by reacting until the free isocyanate was 1.26%.
The obtained polyurethane was charged with 3.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) and allowed to react at 70 to 80 ° C. until the amount of free isocyanate was 0.1% or less. As a result, urethane acrylate B-2 was obtained.
［合成例３］
フラスコにイソホロンジイソシアネート６６６ｇ（３モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが１０００であるポリテトラメチレングリコール（三菱化学社製、品番ＰＴＭＧ－１０００）２０００ｇ（２モル）を仕込み、８０℃にて遊離イソシアネートが３．２％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル１．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－３を得た。 [Synthesis Example 3]
A flask was charged with 666 g (3 mol) of isophorone diisocyanate and 2000 g (2 mol) of polytetramethylene glycol (Mitsubishi Chemical Corporation, product number PTMG-1000) having a number average molecular weight Mn of 1000 as a polyether polyol and released at 80 ° C. Polyurethane was synthesized by reacting until the isocyanate content reached 3.2%.
The obtained polyurethane was charged with 1.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) and allowed to react at 70 to 80 ° C. until the amount of free isocyanate was 0.1% or less. As a result, urethane acrylate B-3 was obtained.
フラスコにイソホロンジイソシアネート６６６ｇ（３モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが１０００であるポリテトラメチレングリコール（三菱化学社製、品番ＰＴＭＧ－１０００）２０００ｇ（２モル）を仕込み、８０℃にて遊離イソシアネートが３．２％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル１．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－３を得た。 [Synthesis Example 3]
A flask was charged with 666 g (3 mol) of isophorone diisocyanate and 2000 g (2 mol) of polytetramethylene glycol (Mitsubishi Chemical Corporation, product number PTMG-1000) having a number average molecular weight Mn of 1000 as a polyether polyol and released at 80 ° C. Polyurethane was synthesized by reacting until the isocyanate content reached 3.2%.
The obtained polyurethane was charged with 1.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) and allowed to react at 70 to 80 ° C. until the amount of free isocyanate was 0.1% or less. As a result, urethane acrylate B-3 was obtained.
［合成例４］
フラスコにイソホロンジイソシアネート８８８ｇ（４モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが１００００であるポリプロピレングリコール（旭硝子社製、品番プレミノールＳ４０１１）１００００ｇ（３モル）を仕込み、８０℃にて遊離イソシアネートが０．２７％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル１５．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－４を得た。 [Synthesis Example 4]
The flask was charged with 888 g (4 mol) of isophorone diisocyanate and 10,000 g (3 mol) of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., product number Preminol S4011) having a number average molecular weight Mn of 10,000 as a polyether polyol. Polyurethane was synthesized by reacting up to 27%.
The obtained polyurethane was charged with 15.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116), and reacted at 70 to 80 ° C. until the free isocyanate content became 0.1% or less. As a result, urethane acrylate B-4 was obtained.
フラスコにイソホロンジイソシアネート８８８ｇ（４モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが１００００であるポリプロピレングリコール（旭硝子社製、品番プレミノールＳ４０１１）１００００ｇ（３モル）を仕込み、８０℃にて遊離イソシアネートが０．２７％までなるまで反応させポリウレタンを合成した。
得られた、ポリウレタンにハイドロキノンモノメチルエーテル１５．５ｇ、２－ヒドロキシエチルアクリレート（分子量１１６）２３２ｇ（２モル）を仕込み、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－４を得た。 [Synthesis Example 4]
The flask was charged with 888 g (4 mol) of isophorone diisocyanate and 10,000 g (3 mol) of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., product number Preminol S4011) having a number average molecular weight Mn of 10,000 as a polyether polyol. Polyurethane was synthesized by reacting up to 27%.
The obtained polyurethane was charged with 15.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116), and reacted at 70 to 80 ° C. until the free isocyanate content became 0.1% or less. As a result, urethane acrylate B-4 was obtained.
［合成例５］
イソシアネート基を含有する（メタ）アクリレートとして２－アクリロイルオキシエチルイソシアネート２８２ｇ（２モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが３０００であるポリブチレングリコール（第一工業製薬社製、品番ＰＢＧ－３０００）３０００ｇ（１モル）、ハイドロキノンモノメチルエーテル１．６４ｇ、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－５を得た。 [Synthesis Example 5]
282 g (2 mol) of 2-acryloyloxyethyl isocyanate as a (meth) acrylate containing an isocyanate group, and polybutylene glycol having a number average molecular weight Mn of 3000 as a polyether polyol (product number PBG-3000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Reaction was carried out at 3000 g (1 mol), 1.64 g of hydroquinone monomethyl ether at 70 to 80 ° C. until the amount of free isocyanate was 0.1% or less to obtain urethane acrylate B-5.
イソシアネート基を含有する（メタ）アクリレートとして２－アクリロイルオキシエチルイソシアネート２８２ｇ（２モル）、ポリエーテルポリオールとして数平均分子量Ｍｎが３０００であるポリブチレングリコール（第一工業製薬社製、品番ＰＢＧ－３０００）３０００ｇ（１モル）、ハイドロキノンモノメチルエーテル１．６４ｇ、７０～８０℃にて遊離イソシアネート量が０．１％以下になるまで反応させ、ウレタンアクリレートＢ－５を得た。 [Synthesis Example 5]
282 g (2 mol) of 2-acryloyloxyethyl isocyanate as a (meth) acrylate containing an isocyanate group, and polybutylene glycol having a number average molecular weight Mn of 3000 as a polyether polyol (product number PBG-3000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Reaction was carried out at 3000 g (1 mol), 1.64 g of hydroquinone monomethyl ether at 70 to 80 ° C. until the amount of free isocyanate was 0.1% or less to obtain urethane acrylate B-5.
（硬化性樹脂組成物の調整）
下記表１記載の各成分と配合量に従って一括で配合し、ディスパーサーで混合攪拌し、硬化型樹脂組成物を得た。
表１に記載した化合物の記号は、以下の化合物を表す。 (Adjustment of curable resin composition)
According to the components and blending amounts shown in Table 1 below, they were blended together and mixed and stirred with a disperser to obtain a curable resin composition.
The symbol of the compound described in Table 1 represents the following compound.
下記表１記載の各成分と配合量に従って一括で配合し、ディスパーサーで混合攪拌し、硬化型樹脂組成物を得た。
表１に記載した化合物の記号は、以下の化合物を表す。 (Adjustment of curable resin composition)
According to the components and blending amounts shown in Table 1 below, they were blended together and mixed and stirred with a disperser to obtain a curable resin composition.
The symbol of the compound described in Table 1 represents the following compound.
（Ｂ－６）（メタ）アクリレート基を有する組成物［商品名「ニューフロンティアＬ－Ｃ９Ａ」第一工業製薬（株）製］
（Ｂ－７）（メタ）アクリレート基を有する組成物［商品名「ＩＳＴＡ」大阪有機化学工業（株）製］
（Ａ－１）共役ジエン系ポリマーポリオール［商品名「ＮＩＳＳＯ－ＰＢ Ｇ－１０００」日本曹達（株）製］
（Ａ－２）共役ジエン系ポリマーポリオール［商品名｛「Ｐｏｌｙｂｄ Ｒ－４５ＨＴ」出光興産（株）製］
（Ａ－３）共役ジエン系ポリマーポリオール［商品名「Ｋｒａｓｏｌ ＬＢＨ３０００」Ｃｒａｙ Ｖａｌｌｅｙ製］
（Ｃ－１）１－ヒドロキシシクロヘキシルフェニルケトン［商品名「ＩＲＧＡＣＵＲＥ１８４」ＢＡＳＦ社製］
（Ｃ－２）２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド［商品名「ＬＵＣＩＲＩＮ ＴＰＯ」ＢＡＳＦ社製］ (B-6) Composition having a (meth) acrylate group [trade name “New Frontier L-C9A” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
(B-7) Composition having (meth) acrylate group [trade name “ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(A-1) Conjugated diene polymer polyol [trade name “NISSO-PB G-1000” manufactured by Nippon Soda Co., Ltd.]
(A-2) Conjugated diene polymer polyol [trade name {“Polybd R-45HT” manufactured by Idemitsu Kosan Co., Ltd.]
(A-3) Conjugated diene polymer polyol [trade name “Krasol LBH3000” manufactured by Cray Valley]
(C-1) 1-hydroxycyclohexyl phenyl ketone [trade name “IRGACURE184” manufactured by BASF Corporation]
(C-2) 2,4,6-trimethylbenzoyldiphenylphosphine oxide [trade name “LUCIRIN TPO” manufactured by BASF Corporation]
（Ｂ－７）（メタ）アクリレート基を有する組成物［商品名「ＩＳＴＡ」大阪有機化学工業（株）製］
（Ａ－１）共役ジエン系ポリマーポリオール［商品名「ＮＩＳＳＯ－ＰＢ Ｇ－１０００」日本曹達（株）製］
（Ａ－２）共役ジエン系ポリマーポリオール［商品名｛「Ｐｏｌｙｂｄ Ｒ－４５ＨＴ」出光興産（株）製］
（Ａ－３）共役ジエン系ポリマーポリオール［商品名「Ｋｒａｓｏｌ ＬＢＨ３０００」Ｃｒａｙ Ｖａｌｌｅｙ製］
（Ｃ－１）１－ヒドロキシシクロヘキシルフェニルケトン［商品名「ＩＲＧＡＣＵＲＥ１８４」ＢＡＳＦ社製］
（Ｃ－２）２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド［商品名「ＬＵＣＩＲＩＮ ＴＰＯ」ＢＡＳＦ社製］ (B-6) Composition having a (meth) acrylate group [trade name “New Frontier L-C9A” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
(B-7) Composition having (meth) acrylate group [trade name “ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(A-1) Conjugated diene polymer polyol [trade name “NISSO-PB G-1000” manufactured by Nippon Soda Co., Ltd.]
(A-2) Conjugated diene polymer polyol [trade name {“Polybd R-45HT” manufactured by Idemitsu Kosan Co., Ltd.]
(A-3) Conjugated diene polymer polyol [trade name “Krasol LBH3000” manufactured by Cray Valley]
(C-1) 1-hydroxycyclohexyl phenyl ketone [trade name “IRGACURE184” manufactured by BASF Corporation]
(C-2) 2,4,6-trimethylbenzoyldiphenylphosphine oxide [trade name “LUCIRIN TPO” manufactured by BASF Corporation]
（硬化物の作成）
硬化型樹脂組成物を３００μｍのスペーサーを４辺に配置した所定寸法のガラス上に滴下し、ガラス板に充填させ、その上から同寸法のガラス板を被せた。
次に、高圧水銀ランプ８０Ｗ／ｃｍを用いて、積算照度５０００ｍＪ／ｃｍ2にて、空気雰囲気下にて照射し硬化し硬化物を得た。 (Creation of cured product)
The curable resin composition was dropped on a glass having a predetermined size in which 300 μm spacers were arranged on four sides, filled in a glass plate, and a glass plate having the same size was covered from above.
Next, using a high-pressure mercury lamp 80 W / cm, it was irradiated with an integrated illuminance of 5000 mJ / cm @ 2 in an air atmosphere and cured to obtain a cured product.
硬化型樹脂組成物を３００μｍのスペーサーを４辺に配置した所定寸法のガラス上に滴下し、ガラス板に充填させ、その上から同寸法のガラス板を被せた。
次に、高圧水銀ランプ８０Ｗ／ｃｍを用いて、積算照度５０００ｍＪ／ｃｍ2にて、空気雰囲気下にて照射し硬化し硬化物を得た。 (Creation of cured product)
The curable resin composition was dropped on a glass having a predetermined size in which 300 μm spacers were arranged on four sides, filled in a glass plate, and a glass plate having the same size was covered from above.
Next, using a high-pressure mercury lamp 80 W / cm, it was irradiated with an integrated illuminance of 5000 mJ / cm @ 2 in an air atmosphere and cured to obtain a cured product.
（硬化性樹脂組成物及び硬化物の評価）
前記硬化性樹脂組成物の透明性、及び前記硬化物の耐熱性、耐熱試験後の黄変性を以下の評価基準に基づいて評価を行った。 (Evaluation of curable resin composition and cured product)
The transparency of the curable resin composition, the heat resistance of the cured product, and the yellowing after the heat test were evaluated based on the following evaluation criteria.
前記硬化性樹脂組成物の透明性、及び前記硬化物の耐熱性、耐熱試験後の黄変性を以下の評価基準に基づいて評価を行った。 (Evaluation of curable resin composition and cured product)
The transparency of the curable resin composition, the heat resistance of the cured product, and the yellowing after the heat test were evaluated based on the following evaluation criteria.
〔透明性〕
硬化型樹脂組成物を目視にて観察し、透明なものを○、白くかすみが生じているものを×として評価した。
〔耐熱性〕
前記硬化物（硬化フィルム）を１１０℃オーブン中に５００時間加熱し、硬化物が流れていないものを○、硬化物が流れているものを×とした。
〔耐熱黄変性〕
前記硬化物（硬化フィルム）を１１０℃オーブン中に５００時間加熱し、加熱後の変色を日本電色工業（株）製 Spectrophotometer SD6000を用いてＹＩ値を測定した。
測定したＹＩが４未満のものを○、４以上のものを×とした。 〔transparency〕
The curable resin composition was visually observed, and a transparent one was evaluated as ◯ and a white haze was evaluated as x.
〔Heat-resistant〕
The cured product (cured film) was heated in an oven at 110 ° C. for 500 hours. The cured product did not flow and the cured product flowed.
[Heat-resistant yellowing]
The cured product (cured film) was heated in an oven at 110 ° C. for 500 hours, and the discoloration after the heating was measured for YI value using a Spectrophotometer SD6000 manufactured by Nippon Denshoku Industries Co., Ltd.
A sample having a measured YI of less than 4 was evaluated as ◯, and a sample having a YI of 4 or more was evaluated as ×.
硬化型樹脂組成物を目視にて観察し、透明なものを○、白くかすみが生じているものを×として評価した。
〔耐熱性〕
前記硬化物（硬化フィルム）を１１０℃オーブン中に５００時間加熱し、硬化物が流れていないものを○、硬化物が流れているものを×とした。
〔耐熱黄変性〕
前記硬化物（硬化フィルム）を１１０℃オーブン中に５００時間加熱し、加熱後の変色を日本電色工業（株）製 Spectrophotometer SD6000を用いてＹＩ値を測定した。
測定したＹＩが４未満のものを○、４以上のものを×とした。 〔transparency〕
The curable resin composition was visually observed, and a transparent one was evaluated as ◯ and a white haze was evaluated as x.
〔Heat-resistant〕
The cured product (cured film) was heated in an oven at 110 ° C. for 500 hours. The cured product did not flow and the cured product flowed.
[Heat-resistant yellowing]
The cured product (cured film) was heated in an oven at 110 ° C. for 500 hours, and the discoloration after the heating was measured for YI value using a Spectrophotometer SD6000 manufactured by Nippon Denshoku Industries Co., Ltd.
A sample having a measured YI of less than 4 was evaluated as ◯, and a sample having a YI of 4 or more was evaluated as ×.
比較例１より共役ジエン系ポリマーポリオールを含まない硬化性樹脂組成物を使用した硬化物は、耐熱黄変性が劣ることが確認できた。
比較例２より（メタ）アクリレート基を有する化合物を含まない硬化性樹脂組成物を使用した硬化物は、耐熱性が劣ることが確認された。
さらに、実施例１～７に記載の共役ジエン系ポリマーポリオール、（メタ）アクリレート基を有する組成物においても、当該の硬化性樹脂組成物を用いると、実施例と同様の透明性および耐熱黄変性に優れる硬化物を得ることを確認している。
From Comparative Example 1, it was confirmed that the cured product using the curable resin composition containing no conjugated diene polymer polyol was inferior in heat yellowing.
From Comparative Example 2, it was confirmed that the cured product using the curable resin composition not containing a compound having a (meth) acrylate group was inferior in heat resistance.
Further, in the conjugated diene polymer polyol and the composition having a (meth) acrylate group described in Examples 1 to 7, when the curable resin composition is used, transparency and heat-resistant yellowing similar to those in Examples are used. It has been confirmed that a cured product having excellent resistance is obtained.
本発明の硬化性樹脂組成物は、粘着性、耐熱黄変性といった性能を有することから、携帯電話、電子書籍、タッチパネル等の電子端末や液晶テレビ、プラズマテレビ、有機ＥＬテレビ等の表示装置の表示パネルと保護板との間の空間の充填剤として用いることができる。
Since the curable resin composition of the present invention has performances such as adhesiveness and heat-resistant yellowing, display of a display device such as an electronic terminal such as a mobile phone, an electronic book or a touch panel, a liquid crystal television, a plasma television, or an organic EL television. It can be used as a filler for the space between the panel and the protective plate.
Claims (3)
- (Ａ)共役ジエン系ポリマーポリオール、及び(Ｂ)（メタ）アクリレート基を有する化合物を含有することを特徴とする硬化性樹脂組成物。 A curable resin composition comprising (A) a conjugated diene polymer polyol and (B) a compound having a (meth) acrylate group.
- 前記（Ａ)共役ジエン系ポリマーポリオールが、１，２－ブタジエン骨格を有することを特徴とする請求項１に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the (A) conjugated diene polymer polyol has a 1,2-butadiene skeleton.
- 前記（Ｂ）（メタ）アクリレート基を有する化合物が、少なくとも、分子中にヒドロキシル基を有するポリマーポリオール（ａ）、および水酸基と反応する置換基を有する（メタ）アクリレートを反応させて得られる化合物であることを特徴とする請求項１又は２に記載の硬化性樹脂組成物。
The compound having the (B) (meth) acrylate group is a compound obtained by reacting at least a polymer polyol (a) having a hydroxyl group in the molecule and a (meth) acrylate having a substituent that reacts with a hydroxyl group. The curable resin composition according to claim 1, wherein the curable resin composition is present.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020167026769A KR20160147728A (en) | 2014-04-16 | 2015-04-08 | Curable resin composition |
| CN201580009739.1A CN106029703A (en) | 2014-04-16 | 2015-04-08 | Curable resin composition |
| JP2016513734A JPWO2015159769A1 (en) | 2014-04-16 | 2015-04-08 | Curable resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014084590 | 2014-04-16 | ||
| JP2014-084590 | 2014-04-16 |
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| WO2015159769A1 true WO2015159769A1 (en) | 2015-10-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2015/060930 WO2015159769A1 (en) | 2014-04-16 | 2015-04-08 | Curable resin composition |
Country Status (5)
| Country | Link |
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| JP (1) | JPWO2015159769A1 (en) |
| KR (1) | KR20160147728A (en) |
| CN (1) | CN106029703A (en) |
| TW (1) | TWI527837B (en) |
| WO (1) | WO2015159769A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017048358A (en) * | 2015-09-01 | 2017-03-09 | デクセリアルズ株式会社 | Photocurable resin composition and method for producing picture display device |
| WO2017038845A1 (en) * | 2015-09-01 | 2017-03-09 | デクセリアルズ株式会社 | Photocurable resin composition and method for manufacturing image display device |
| CN113015621A (en) * | 2018-11-16 | 2021-06-22 | 3M创新有限公司 | Curable compositions, articles made therefrom, and methods of making and using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210097043A (en) * | 2020-01-29 | 2021-08-06 | 아라까와 가가꾸 고교 가부시끼가이샤 | Thermosetting peeling coating agent, cured product, and thermosetting peeling film and production method thereof |
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| JPH11286673A (en) * | 1998-04-01 | 1999-10-19 | Sanyo Chem Ind Ltd | Moisture-curable urethane adhesive |
| JP2006342222A (en) * | 2005-06-08 | 2006-12-21 | Mitsuyoshi Sato | Light-curable resin composition |
| JP2012144634A (en) * | 2011-01-12 | 2012-08-02 | Jsr Corp | Optical resin and method for producing optical resin layer, composition for optical resin, and image display device |
| WO2013187508A1 (en) * | 2012-06-15 | 2013-12-19 | 昭和電工株式会社 | Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for manufacturing image display device |
| JP2014203265A (en) * | 2013-04-04 | 2014-10-27 | 昭和電工株式会社 | Manufacturing method for image display device and image display device manufactured by manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5757292B2 (en) * | 2010-12-08 | 2015-07-29 | 旭硝子株式会社 | Transparent surface material with adhesive layer, display device and manufacturing method thereof |
| JP5738641B2 (en) | 2011-03-25 | 2015-06-24 | 株式会社日本触媒 | Optical UV-curable resin composition, cured product, and display device |
| JP5642028B2 (en) * | 2011-07-06 | 2014-12-17 | 株式会社日本触媒 | Optical UV-curable resin composition, cured product, and display device |
| JP6067235B2 (en) * | 2012-03-06 | 2017-01-25 | 第一工業製薬株式会社 | Urethane (meth) acrylate and curable resin composition containing the same |
-
2015
- 2015-04-08 WO PCT/JP2015/060930 patent/WO2015159769A1/en active Application Filing
- 2015-04-08 KR KR1020167026769A patent/KR20160147728A/en unknown
- 2015-04-08 CN CN201580009739.1A patent/CN106029703A/en active Pending
- 2015-04-08 JP JP2016513734A patent/JPWO2015159769A1/en active Pending
- 2015-04-14 TW TW104111991A patent/TWI527837B/en not_active IP Right Cessation
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|---|---|---|---|---|
| JPH11286673A (en) * | 1998-04-01 | 1999-10-19 | Sanyo Chem Ind Ltd | Moisture-curable urethane adhesive |
| JP2006342222A (en) * | 2005-06-08 | 2006-12-21 | Mitsuyoshi Sato | Light-curable resin composition |
| JP2012144634A (en) * | 2011-01-12 | 2012-08-02 | Jsr Corp | Optical resin and method for producing optical resin layer, composition for optical resin, and image display device |
| WO2013187508A1 (en) * | 2012-06-15 | 2013-12-19 | 昭和電工株式会社 | Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for manufacturing image display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017048358A (en) * | 2015-09-01 | 2017-03-09 | デクセリアルズ株式会社 | Photocurable resin composition and method for producing picture display device |
| WO2017038845A1 (en) * | 2015-09-01 | 2017-03-09 | デクセリアルズ株式会社 | Photocurable resin composition and method for manufacturing image display device |
| CN113015621A (en) * | 2018-11-16 | 2021-06-22 | 3M创新有限公司 | Curable compositions, articles made therefrom, and methods of making and using the same |
| CN113015621B (en) * | 2018-11-16 | 2023-09-29 | 3M创新有限公司 | Curable compositions, articles made therefrom, and methods of making and using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106029703A (en) | 2016-10-12 |
| TW201540738A (en) | 2015-11-01 |
| TWI527837B (en) | 2016-04-01 |
| JPWO2015159769A1 (en) | 2017-04-13 |
| KR20160147728A (en) | 2016-12-23 |
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