Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
• • 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
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/067—Polyurethanes; Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6204—Polymers of olefins
  • C08G18/6208—Hydrogenated polymers of conjugated dienes

Definitions

• the present invention relates to a photocurable resin and a photocurable resin composition.
• Patent Document 1 states that “a polyol having a hydrogenated polybutadiene skeleton in the main chain is made to have a high molecular weight using a polyfunctional compound, and then the high molecular weight water having a molecular weight of 10,000 to 100,000 is obtained.
• Patent Document 2 discloses that “a photocurable resin composition containing a hydrogenated butadiene-based polymer having a plurality of photocurable functional groups, a monomer having a single photocurable functional group, and a photopolymerization initiator”.
• the pressure-sensitive adhesive sheet is characterized by comprising a cured product of "(Claim 1)".
• the photocurable resin composition using the photocurable resin (urethane (meth) acrylate oligomer, hydrogenated butadiene-based polymer) described in Patent Documents 1 and 2 may have low adhesive strength. In particular, it became clear that the adhesive strength under high temperature and high humidity was inferior.
• an object of the present invention is to provide a photocurable resin composition having high adhesive strength and good adhesion under high temperature and high humidity, and a photocurable resin used therefor.
• the present inventors have a (meth) acryloyloxy group at a terminal via a predetermined urethane bond and a repeating unit derived from a 1,2-butadiene skeleton in the main chain skeleton.
• a photocurable resin having a specific ratio and having two or more urethane bonds By using a photocurable resin having a specific ratio and having two or more urethane bonds, a photocurable resin composition having high adhesive strength and good adhesion under high temperature and high humidity is obtained.
• the present invention has been completed. That is, it has been found that the above problem can be solved by the following configuration.
• a photocurable resin having at least a repeating unit represented by the following formula (Ib) among repeating units represented by the following formulas (Ia) to (Ic) in the main chain skeleton The content of the repeating unit represented by the following formula (Ia) is 0 to 40 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic), The content of the repeating unit represented by the following formula (Ib) is 60 to 100 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic), The content of the repeating unit represented by the following formula (Ic) is 0 to 10 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic), At least one of the terminals has a structure represented by the following formula (IIa) or the following formula (IIb); A photocurable resin having at least two urethane bonds represented by the following formula (III) in the main chain skeleton.
• each R 1 is independently a hydrogen atom or Represents a methyl group
• n represents an integer of 1 to 7
• * represents a bonding position with the main chain.
• a photocurable resin composition comprising the photocurable resin according to (1) above, a monofunctional (meth) acrylate compound having one (meth) acryloyloxy group, and a photopolymerization initiator.
• the photocurable resin of the present invention has a specific amount of a predetermined repeating unit represented by the formula (Ib) described later in the main chain skeleton, and the formula (IIa) or the formula (IIb) described later at at least one of the terminals. And a photocurable resin having at least two urethane bonds represented by the formula (III) described later in the main chain skeleton.
• the photocurable resin of the present invention has at least a repeating unit represented by the following formula (Ib) among repeating units represented by the following formulas (Ia) to (Ic) in the main chain skeleton.
• the content of the repeating unit represented by the following formula (Ia) is 0 to 40 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic). It is preferably 30 mol%.
• the content of the repeating unit represented by the following formula (Ib) is 60 to 100 mol%, and 65 to 95 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic).
• the content of the repeating unit represented by the following formula (Ic) is 0 to 10 mol% with respect to all the repeating units represented by the following formulas (Ia) to (Ic), and 0 to 5 mol%. Is preferred.
• the double line between the broken line and the solid line represents a single bond or a double bond.
• mol% with respect to all repeating units refers to a value calculated from the charging ratio of monomers (1,3-butadiene, 1,2-butadiene, styrene).
• the arrangement of the repeating units represented by the above formulas (Ia) to (Ic) may be arranged randomly, arranged in blocks, or a mixture of both. .
• the adhesiveness under high temperature and high humidity is good.
• a light-curable resin composition This is presumably because the crystal structure is not adopted, the flexibility is good, and the dimensional change of the substrate can be followed even under high temperature and high humidity. As shown in Comparative Example 5 described later, this is a result of not satisfying the mol% of the repeating unit represented by the above formula (Ib), that is, many repeating units represented by the above formula (Ia). If included, the photocurable resin takes a crystal structure and the viscosity increases, so that a diluent is required, and as a result, it can be inferred from the result that the adhesiveness is lowered.
• the photocurable resin of the present invention has at least two urethane bonds represented by the following formula (III) in the main chain skeleton.
• the urethane bond represented by the above formula (III) is a urethane bond contained in the main chain skeleton, unlike the urethane bond contained in the terminal structure described later.
• a urethane bond contained in the structure represented by the following formula (IIIa) produced when a hydrogenated polybutadiene polymer having hydroxyl groups at both ends and a diisocyanate compound having two isocyanate groups are reacted (dimerized); When reacting (trimerizing) a hydrogenated polybutadiene-based polymer having hydroxyl groups at both ends and a triisocyanate compound having three isocyanate groups (for example, a biuret, isocyanurate, and attack of a diisocyanate compound). It is preferably a urethane bond contained in the structure represented by the following formula (IIIb) to be generated.
• R 2 represents a residue excluding the isocyanate group of the diisocyanate compound, * represents a bonding position with the main chain
• R 3 represents an isocyanate of triisocyanate. Represents a residue excluding a group, and * represents a bonding position with the main chain.
• this invention becomes a photocurable resin composition with high adhesive strength by using the photocurable resin which has two or more of such urethane bonds in the principal chain skeleton.
• the photocurable resin which has two or more of such urethane bonds in the principal chain skeleton.
• hydrogen bonds are formed between the N—H groups of the urethane bond contained in the main chain skeleton of the adjacent photocurable resin. This is thought to be because it is more likely to occur.
• This can also be inferred from the results when the main chain skeleton does not have a urethane bond, as shown in Comparative Example 6 described later.
• the number of urethane bonds in the main chain skeleton is 2 to 10 because the adhesive strength and the physical properties of the cured product become higher.
• the photocurable resin of the present invention has a structure represented by the following formula (IIa) or the following formula (IIb) at at least one of the terminals.
• R 1 each independently represents a hydrogen atom or a methyl group.
• n represents an integer of 1 to 7
• the formulas (IIa) and (IIb) in the formula (IIb) a plurality of R 1 may be the same or different.
• a photocurable resin composition having high adhesive strength and good adhesiveness under high temperature and high humidity is obtained.
• the degree of polymerization (crosslink density) after photocuring is unexpectedly increased, and the electron donation of the amino group This is thought to be because radicals were easily generated due to the nature. This can be inferred from the result that the degree of polymerization is low and the adhesive strength is poor when the terminal has a structure represented by the following formula (IV) as shown in Comparative Examples 1 to 3 described later. .
• R 1 represents a hydrogen atom or a methyl group
• * represents a bonding position with the main chain.
• the terminal structure represented by the above formula (IIa) or the above formula (IIb) is 2 for the reason that the adhesiveness under high temperature and high humidity becomes better and the elongation of the cured product becomes better. It is preferable to have at least one, and it is more preferable to have two or more terminal structures represented by the above formula (IIa).
• the method for preparing the photocurable resin of the present invention is not particularly limited.
• a hydrogenated polybutadiene polymer having a hydroxyl group at the terminal hereinafter referred to as “hydroxyl-terminated hydrogenated polybutadiene (a)”
• an isocyanate group an isocyanate group
• a method of reacting the compound (b) having a (meth) acryloyloxy group with the polyisocyanate compound (c) having two or more isocyanate groups is preferred, and more specifically, the hydroxyl group-terminated hydrogenated polybutadiene (a) and The hydroxyl group remaining after the polyisocyanate compound (c) is reacted with a hydroxyl group-isocyanate group equivalent ratio (hydroxyl group / isocyanate group) greater than 1 (for example, 1.1 to 2) to increase the molecular weight.
• the isocyanate group of compound (b) are reacted to introduce a (meth) acryloyloxy group.
• the “(meth) acryloyloxy group” means an acryloyloxy group and / or a methacryloyloxy group.
• hydroxyl group-terminated hydrogenated polybutadiene (a) is, for example, represented by the following formulas (a1) and (a2) from the viewpoint of satisfying the mol% of the repeating units represented by the formulas (Ia) to (Ic). Suitable examples include both-end hydroxylated polybutadiene.
• m represents an integer of 15 to 90.
• the number average molecular weight of the hydrogenated polybutadiene polymer (a) is preferably from 1000 to 10,000, and more preferably from 1500 to 5,000.
• the number average molecular weight is a value determined by gel permeation chromatography (GPC) measurement in terms of polystyrene.
• R 1 each independently represents a hydrogen atom or a methyl group, and in formula (b1), n represents an integer of 1 to 7. In formula (b2), R 1 may be the same or different.
• the polyisocyanate compound (C) is not particularly limited as long as it has two isocyanate groups in the molecule.
• Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI ( For example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetra Aromatic diisocyanates such as methylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; hex
• the photocurable resin composition of the present invention is a monofunctional resin having the above-described photocurable resin of the present invention (hereinafter also referred to as “photocurable resin (A)”) and one (meth) acryloyloxy group. It is a photocurable resin composition containing a (meth) acrylate compound (B) and a photopolymerization initiator (C).
• the photocurable resin (A) is the same as the photocurable resin of the present invention described above, but the content of the photocurable resin (A) in the photocurable resin composition of the present invention is 10 to It is preferably 80% by mass, more preferably 20 to 65% by mass.
• the monofunctional (meth) acrylate compound (B) is not particularly limited as long as it is a compound having one (meth) acryloyloxy group. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, carbitol (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate , Stearyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, allyl (meth) acrylate, 3-methoxybutyl (meth)
• the compatibility with the photocurable resin (A) is good, and because of excellent weather resistance, it is dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate. Is preferred.
• the content of the monofunctional (meth) acrylate compound (B) is preferably 10 to 200 parts by mass, and 30 to 100 parts by mass with respect to 100 parts by mass of the photocurable resin (A). Is more preferable.
• Photopolymerization initiator (C) examples include carbonyl compounds such as alkylphenone compounds, benzoin ether compounds, and benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like. .
• acetophenone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -Phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, the following formula (1)
• a carbonyl compound such as 1-hydroxycyclohexyl phenyl ketone; a sulfur compound such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobisisobutyronitrite And azo compounds such as azobis-2,4-di
• 1-hydroxycyclohexyl phenyl ketone 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one are preferred.
• Examples of commercially available 1-hydroxycyclohexyl phenyl ketone include Irgacure 184 (manufactured by Ciba Specialty Chemicals).
• the content of the photopolymerization initiator (C) is preferably 1 to 10 parts by mass and more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the photocurable resin (A).
• the photocurable resin composition of the present invention preferably uses an ester group-containing (meth) acrylate (D) represented by the following formula because the toughness after curing is good.
• R 1 represents a hydrogen atom or a methyl group
• R 3 represents an alkylene group having 2 to 6 carbon atoms
• r represents an integer of 3 to 8
• s represents an integer of 1 to 5
• ester group-containing (meth) acrylates (D) are commercially available products such as “Placcel FA-1”, “Placcel FA-2”, “Placcel FA-2D”, “Placcel FA-3”, “Placcel” FA-4, Plaxel FA-5, Plaxel FM-1, Plaxel FM-2, Plaxel FM-2D, Plaxel FM-3, Plaxel FM-4, Plaxel FM ⁇ 5 ”(all manufactured by Daicel Chemical Industries, Ltd.) and the like can be used.
• the content of the ester group-containing (meth) acrylate (D) is preferably 1 to 50 parts by mass, and preferably 5 to 20 parts by mass with respect to 100 parts by mass of the photocurable resin (A). More preferred.
• the photocurable resin composition of the present invention may contain a solvent from the viewpoint of workability.
• the solvent include ethanol, isopropanol, butanol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and cyclohexanone.
• the photocurable resin composition of the present invention has various additives such as a filler, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, and adhesiveness, as long as the object of the present invention is not impaired.
• An imparting agent, a leveling agent, a dispersant, an antifoaming agent, a matting agent, a light stabilizer (for example, a hindered amine compound), a dye, a pigment, and the like can be contained.
• the method for preparing the photocurable resin composition of the present invention is not particularly limited.
• the above-mentioned essential components and optional components are placed in a reaction vessel, and are sufficiently kneaded using a stirrer such as a mixing mixer under reduced pressure. It can manufacture by the method to do.
• the synthesized photocurable resin (A-1) has a content of the repeating unit represented by the above formula (Ia) of 15 to the total repeating units represented by the above formulas (Ia) to (Ic).
• the synthesized photocurable resin (A-2) has a content of the repeating unit represented by the above formula (Ia) of 15 to the total repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by formula (IIa) (R 1 in formula (IIa) was a hydrogen atom) and had two urethane bonds represented by formula (III).
• the synthesized photocurable resin (A-3) has a content of the repeating unit represented by the above formula (Ia) of 15 to the total repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) was a hydrogen atom) and had four urethane bonds represented by the formula (III).
• the content of the repeating unit represented by the above formula (Ia) is 15% with respect to all the repeating units represented by the above formulas (Ia) to (Ic).
• the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) was a hydrogen atom) and had four urethane bonds represented by the formula (III).
• the synthesized photocurable resin (A-5) has a content of the repeating unit represented by the above formula (Ia) of 15 to the total repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIb) (R 1 in the formula (IIb) was a hydrogen atom) and four urethane bonds represented by the above formula (III).
• the synthesized photocurable resin (A-6) has a content of the repeating unit represented by the above formula (Ia) of 14 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 80.75 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). The content of the repeating unit represented by the above formula (Ic) is 5 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic), and is represented by the above formula (IIa). It was confirmed that the terminal structure (R 1 in the formula (IIa) is a hydrogen atom) and four urethane bonds represented by the formula (III) are included.
• the synthesized photocurable resin (A-7) has a content of the repeating unit represented by the above formula (Ib) of 100 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It has a terminal structure represented by the above formula (IIa) (R 1 in formula (IIa) is a hydrogen atom), and has four urethane bonds represented by the above formula (III). I confirmed that
• the synthesized photocurable resin (E-1) has a content of the repeating unit represented by the above formula (Ia) of 80 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the formula (Ib) is 20 mol% with respect to all the repeating units represented by the formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IV) (R 1 in the formula (IV) was a hydrogen atom) and had 6 urethane bonds represented by the formula (III).
• the synthesized photocurable resin (E-2) has a content of the repeating unit represented by the above formula (Ia) of 15 to the total repeating units represented by the above formulas (Ia) to (Ic).
• the synthesized photocurable resin (E-3) has a content of the repeating unit represented by the above formula (Ia) of 15 to the total repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by formula (IV) (R 1 in formula (IV) was a hydrogen atom) and had two urethane bonds represented by formula (III).
• the synthesized photocurable resin (E-4) has a content of the repeating unit represented by the above formula (Ia) of 80 with respect to all the repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the formula (Ib) is 20 mol% with respect to all the repeating units represented by the formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) is a hydrogen atom) and did not have a urethane bond represented by the above formula (III).
• the synthesized photocurable resin (E-5) has a content of repeating units represented by the above formula (Ia) of 80 with respect to all repeating units represented by the above formulas (Ia) to (Ic). And the content of the repeating unit represented by the formula (Ib) is 20 mol% with respect to all the repeating units represented by the formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) was a hydrogen atom) and had four urethane bonds represented by the formula (III).
• the content of the repeating unit represented by the above formula (Ib) is 85 mol% with respect to all the repeating units represented by the above formulas (Ia) to (Ic). It was confirmed that it had a terminal structure represented by the formula (IIa) (R 1 in the formula (IIa) is a hydrogen atom) and did not have a urethane bond represented by the above formula (III).
• Examples 1 to 10, Comparative Examples 1 to 6 Each component shown in the following Table 1 was mixed using a stirrer with the composition (parts by mass) shown in Table 1 to obtain each photocurable resin composition shown in Table 1. Subsequently, the hardened
• a light irradiation device GS UVSYSTEM TYPE S250-01, manufactured by GS Yuasa Lighting Co., Ltd.
• a metal hydrolamp is used as a light source, and an ultraviolet ray having a wavelength of 250 to 380 nm is a light amount of 120 mW / cm and an integrated light amount of 1000 mJ / cm 2. Irradiated to obtain a cured product.
• Monofunctional acrylate (B-1) Dicyclopentenyl acrylate
• Monofunctional acrylate (B-2) Isobornyl acrylate
• Monofunctional acrylate (B-3) Isodecyl acrylate
• D-1 Unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone (Placcel FM1, manufactured by Daicel Corporation)
• Ester group-containing acrylate (D-2) Unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone (Placcel FM3, manufactured by Daicel)
• the photocurable resin having the terminal structure represented by the formula (IV) is used regardless of the mol% of the repeating unit represented by the formula (Ib) in the main chain skeleton. It was found that the degree of polymerization was low, the adhesive strength was inferior, and the adhesive strength under high temperature and high humidity was also low (Comparative Examples 1 to 3).
• the main chain skeleton has a repeating unit represented by the above formula (Ib) at a specific ratio, has a terminal structure represented by the above formula (IIa) or the above formula (IIb), and the main clavicle.
• a photocurable resin (A) having at least two urethane bonds the degree of polymerization is high, the adhesive strength is high, and the adhesiveness under high temperature and high humidity is also good. (Examples 1 to 10).

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