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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- acrylate
- meth
- resin composition
- curable resin
- conjugated diene
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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
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
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
Description
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).
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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、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、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.
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.
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.
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.
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.
[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.
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.
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.
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-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.
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.
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.
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.
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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 |
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 |
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 |
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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 |
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