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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
  • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
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  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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  • 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
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  • C08F290/062—Polyethers
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  • 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
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
  • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
  • C08G18/168—Organic compounds
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  • 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
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  • 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
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/69—Polymers of conjugated dienes
• • 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
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
• • 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
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a polycarbodiimide compound, a resin composition containing the polycarbodiimide compound, and a cured product of the resin composition.
• polycarbodiimide compounds are widely used as hydrolysis stabilizers for compounds containing ester groups and as crosslinking agents for resins containing carboxy groups, etc., which are groups that can react with carbodiimide groups. It is used.
• Patent Document 1 describes a compound in which 2-hydroxyethyl acrylate or the like is added to carbodiimide.
• Patent Document 2 describes a carbodiimide compound in which a polybutadiene chain is introduced as a side chain of a carbodiimide compound by reacting the functional group of a polybutadiene compound having a functional group that reacts with a carbodiimide group with the carbodiimide group of the carbodiimide compound. is listed.
• Patent Document 3 describes a polycarbodiimide copolymer having a soft segment derived from a polyol and a hard segment derived from an aromatic polycarbodiimide.
• the present invention provides a polycarbodiimide compound that has an excellent effect of improving the water resistance of a resin having a (meth)acryloyl group, a resin having a (meth)acryloyl group, and a resin containing the polycarbodiimide compound and having excellent water resistance.
• the present invention aims to provide a composition and a cured product of the resin composition.
• the present invention provides the following [1] to [14].
• polycarbodiimide compound according to [1] or [2] above, wherein the polycarbodiimide (a) has a theoretical molecular weight of 400 to 8,000.
• At least one selected from the aliphatic diisocyanate and alicyclic diisocyanate is at least one selected from dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate, [ The polycarbodiimide compound according to any one of [1] to [3].
• the functional group of the polymer (b) that can react with the isocyanate group is at least one selected from isocyanate groups, hydroxyl groups, amino groups, and carboxy groups, as described in [1] to [6] above.
• the blending amount of the polycarbodiimide (a) is 20 to 80% by mass in 100% by mass of the total blending amount of the polycarbodiimide (a), the polymer (b), and the compound (c).
• the functional group capable of reacting with the isocyanate group of the compound (c) is at least one selected from an isocyanate group, a hydroxyl group, an amino group, and a carboxy group, as described in [8] or [9] above. polycarbodiimide compound.
• Polycarbodiimide (a) obtained by polymerizing at least one selected from aliphatic diisocyanates and alicyclic diisocyanates and having isocyanate groups at both ends, and A reaction product of a polymer (b) which is at least one polymer selected from butadiene and isoprene or a hydrogenated product thereof and has a functional group capable of reacting with an isocyanate group,
• a method for producing a polycarbodiimide compound which comprises reacting the polycarbodiimide (a) and the polymer (b) at 120°C or lower.
• Polycarbodiimide (a) obtained by polymerizing at least one selected from aliphatic diisocyanates and alicyclic diisocyanates and having isocyanate groups at both ends; A polymer (b) which is at least one polymer selected from butadiene and isoprene or a hydrogenated product thereof and has a functional group capable of reacting with an isocyanate group, and Compound (c) having a (meth)acryloyl group and a functional group capable of reacting with an isocyanate group A method for producing a polycarbodiimide compound which is a reaction product of A method for producing a polycarbodiimide compound, comprising reacting the polycarbodiimide (a), the polymer (b), and the compound (c) at 120°C or lower.
• Polycarbodiimide (a) obtained by polymerizing at least one selected from aliphatic diisocyanates and alicyclic diisocyanates and having isocyanate groups at both ends, and A reaction product of a polymer (b) which is at least one polymer selected from butadiene and isoprene or a hydrogenated product thereof and has a functional group capable of reacting with an isocyanate group,
• a method for producing a polycarbodiimide compound which comprises reacting the polycarbodiimide (a) and the polymer (b) in a solvent.
• Polycarbodiimide (a) obtained by polymerizing at least one selected from aliphatic diisocyanates and alicyclic diisocyanates and having isocyanate groups at both ends; A polymer (b) which is at least one polymer selected from butadiene and isoprene or a hydrogenated product thereof and has a functional group capable of reacting with an isocyanate group, and Compound (c) having a (meth)acryloyl group and a functional group capable of reacting with an isocyanate group A reaction product of A method for producing a polycarbodiimide compound, which comprises reacting the polycarbodiimide (a), the polymer (b), and the compound (c) in a solvent.
• a polycarbodiimide compound that is excellent in improving the water resistance of a resin having a (meth)acryloyl group. Further, according to the present invention, it is possible to provide a resin composition containing the polycarbodiimide compound and having a (meth)acryloyl group and having excellent water resistance, and a cured product thereof.
• (meth)acryloyl group means an acryloyl group or a methacryloyl group.
• the polycarbodiimide compound according to the present invention is a polycarbodiimide (a) obtained by polymerizing at least one selected from aliphatic diisocyanates and alicyclic diisocyanates and having isocyanate groups at both ends, and Polymer (b) which is at least one polymer selected from butadiene and isoprene or a hydrogenated product thereof, and which has a functional group capable of reacting with an isocyanate group. It is a polycarbodiimide compound which is a reaction product of
• the polycarbodiimide compound is a polymer of at least one kind selected from butadiene and isoprene or a hydrogenated product thereof, and has a structure mainly derived from a polymer (b) having a functional group capable of reacting with an isocyanate group. Have it on the chain.
• the polymer (b) facilitates the compatibilization of the polycarbodiimide compound and the (meth)acryloyl group-containing resin (D), and therefore, the obtained cured product is capable of compatibility between the polycarbodiimide compound and the (meth)acryloyl group-containing resin (D) even under high temperature and high humidity conditions.
• a uniform structure in which the resin (D) having an acryloyl group is compatible can be maintained.
• the polymer (b) since the polymer (b) is incorporated into the crosslinked structure without inhibiting the reactivity of the polycarbodiimide group, it has the excellent effect of improving the strength, water resistance, durability, etc. of the cured product. . Furthermore, since the polymer (b) has a functional group that can react with the isocyanate group, when the polymer (b) is bonded to the polycarbodiimide (a), the polymer (b) has a functional group that can react with the isocyanate group. The groups will be bonded to the terminal isocyanate groups of polycarbodiimide (a).
• the carbodiimide groups of the polycarbodiimide (a) are prevented from bonding with the polymer (b) and the number of carbodiimide groups is reduced, and the above-mentioned effects due to the carbodiimide groups are prevented from decreasing.
• the polycarbodiimide compound is a reaction product of the polycarbodiimide (a), the polymer (b), and a compound (c) having a (meth)acryloyl group and a functional group capable of reacting with an isocyanate group. It is preferable that there be.
• the polycarbodiimide compound has a (meth)acryloyl group and can react with the resin (D) having a (meth)acryloyl group, so that the carbodiimide group can be uniformly distributed in the cured product, As a result, water resistance is improved.
• Polycarbodiimide (a) is a polycarbodiimide obtained by polymerizing at least one selected from aliphatic diisocyanates and alicyclic diisocyanates, and has isocyanate groups at both ends.
• the aliphatic diisocyanate means a diisocyanate in which each of two isocyanate groups is bonded to a carbon constituting the aliphatic hydrocarbon structure.
• an alicyclic diisocyanate is one in which each of the two isocyanate groups is bonded to a carbon constituting the aliphatic hydrocarbon structure or the alicyclic hydrocarbon structure, and the two isocyanate groups are It means a diisocyanate in which at least one carbon is a carbon forming an alicyclic hydrocarbon structure.
• the alicyclic diisocyanate is preferably a diisocyanate in which each of the two isocyanate groups is bonded to a carbon constituting the alicyclic hydrocarbon structure.
• aliphatic diisocyanates include hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), and 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1 ]Heptane, tetramethylxylylene diisocyanate (TMXDI), and the like.
• alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), methylcyclohexane diisocyanate (1-methylcyclohexane-2,4-diyl diisocyanate), and the like.
• dicyclohexylmethane-4,4'-diisocyanate (HMDI) and tetrahydrol are preferred from the viewpoint of ease of synthesis of the polycarbodiimide compound, storage stability of the synthesized polycarbodiimide compound, and effect of improving the water resistance of the resin.
• Methyl xylylene diisocyanate (TMXDI) and isophorone diisocyanate (IPDI) are preferred, and dicyclohexylmethane-4,4'-diisocyanate (HMDI) is more preferred from the viewpoint of storage stability and reactivity of carbodiimide groups.
• the degree of polymerization of polycarbodiimide (a) is preferably 20 or less, more preferably 15 or less, still more preferably 13 or less, even more preferably 9 or less, from the viewpoint of preventing gelation during synthesis of the polycarbodiimide compound. Further, from the viewpoint of reactivity with the resin, the degree of polymerization is preferably 2 or more, more preferably 3 or more. Furthermore, from the viewpoint of improving the water resistance of the resin, the degree of polymerization is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 13, even more preferably 3 to 9. The most preferred range is 5-9. The degree of polymerization can be measured by the method described in Examples.
• the degree of polymerization of polycarbodiimide (a) represents the number of carbodiimide groups in polycarbodiimide (precursor of polycarbodiimide compound) having isocyanate groups at both ends obtained by polymerizing a diisocyanate compound.
• the degree of polymerization n of a polycarbodiimide having two carbodiimide groups obtained by polymerizing three diisocyanate compounds is 2.
• the theoretical molecular weight of the polycarbodiimide (a) is preferably 400 to 8,000, more preferably 500 to 6,000, even more preferably 600 to 4,000, and even more preferably 600 to 3,000. 500, and even more preferably 600 to 3,000. Note that the theoretical molecular weight can be calculated based on the molecular weight and degree of polymerization of the raw material diisocyanate compound.
• the method for producing polycarbodiimide (a) is not particularly limited, and any known production method can be used. For example, the synthesis methods shown in (a1) to (a3) below may be mentioned.
• (a1) A diisocyanate compound is carbodiimidized in the presence of a catalyst to obtain an isocyanate-terminated polycarbodiimide compound, and then an organic compound (terminal capping agent) having a functional group that can react with an isocyanate group is added.
• (a2) A diisocyanate compound and an organic compound having a functional group capable of reacting with the isocyanate group (end-capping agent) are mixed, and a carbodiimidization reaction and an end-capping reaction are carried out in the presence of a catalyst.
• the carbodiimidization reaction is preferably, for example, polymerization (decarboxylation condensation reaction) of a diisocyanate compound in the presence of a carbodiimidization catalyst (U.S. Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, J. (See Org. Chem.
• Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3 -Methyl-2-phospholene-1-oxide and 3-phosphorene isomers thereof.
• 3-methyl-1-phenyl-2-phosphorene-1-oxide is preferred from the viewpoint of reactivity and availability.
• the amount of the carbodiimidization catalyst used is usually preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.07 to 5 parts by weight, based on 100 parts by weight of the diisocyanate compound. 3 parts by mass.
• the polymer (b) is at least one polymer selected from butadiene and isoprene or a hydrogenated product thereof, and is a polymer having a functional group capable of reacting with an isocyanate group. Since the polymer (b) has a functional group that can react with an isocyanate group, the functional group reacts with the isocyanate group present at the end of the polycarbodiimide (a). Therefore, when reacting the polymer (b) with the polycarbodiimide (a), reaction between the terminal end of the polymer (b) and the carbodiimide group in the polycarbodiimide (a) is avoided.
• the carbodiimide equivalent weight of the obtained polycarbodiimide compound can be increased.
• the end of the polymer (b) and the carbodiimide group in the polycarbodiimide (a) react to form a butadiene structure or an isoprene structure in the side chain of the polycarbodiimide compound, and the reaction of the carbodiimide groups present in the vicinity is also prevented from being alienated by the butadiene or isoprene structure.
• the polymer (b) is preferably a polymer of butadiene (polybutadiene) or a hydrogenated product thereof, or a polymer of isoprene (polyisoprene) or a hydrogenated product thereof, and a polymer having a functional group capable of reacting with an isocyanate group. More preferably, it is a polymer of butadiene (polybutadiene) or a hydrogenated product thereof, and has a functional group capable of reacting with an isocyanate group.
• the above polymer (b) is more preferably an unhydrogenated product of the polymer from the viewpoint of improving the water resistance of the resin.
• Examples of functional groups that can react with isocyanate groups include isocyanate groups, hydroxyl groups, amino groups, and carboxy groups. , preferably a hydroxyl group.
• the number average molecular weight of the polymer (b) is preferably 500 to 5,000, more preferably 1,000 to 4,000, even more preferably 1,000 to 3,500, even more preferably is from 1,000 to 3,000, more preferably from 1,200 to 2,500.
• the number average molecular weight is 500 or more, it can be expected that the compatibility with the resin (D) having a (meth)acryloyl group will increase and the effect of improving water resistance will increase. If it is 5,000 or less, the ratio of carbodiimide groups in the molecule is high, so the effect due to carbodiimide groups becomes high.
• the number average molecular weight can be measured by the method described in Examples.
• the number of functional groups capable of reacting with isocyanate groups per molecule of the polymer (b) is 1 or 2 or more, and from the viewpoint of good storage stability of the carbodiimide compound and ease of production, Preferably the number is two or more, more preferably two.
• Compound (c) is a compound having a (meth)acryloyl group and a functional group capable of reacting with an isocyanate group.
• the polycarbodiimide compound has a structural unit derived from the compound (c)
• the polycarbodiimide compound since the polycarbodiimide compound has a (meth)acryloyl group, it can react with the resin (D) having a (meth)acryloyl group, Carbodiimide groups can be uniformly distributed in the cured product, resulting in improved water resistance.
• functional groups that can react with isocyanate groups include isocyanate groups, hydroxyl groups, amino groups, carboxy groups, etc. From the viewpoint of ease of production, ease of obtaining raw materials, and good storage stability of carbodiimide compounds, Preferably it is a hydroxyl group.
• the number of (meth)acryloyl groups per molecule of compound (c) is one or more, and preferably three or less.
• the number of functional groups capable of reacting with isocyanate groups per molecule of compound (c) is 1 or 2 or more, ease of production, ease of obtaining raw materials, and good storage stability of the carbodiimide compound. From this point of view, the number is preferably one or two, and more preferably one.
• Compound (c) is preferably monohydroxyalkyl (meth)acrylate. Further, the compound (c) is preferably a (meth)acrylate containing one hydroxyl group (hereinafter referred to as "hydroxyl group-containing (meth)acrylate”), and more preferably a hydroxyl group-containing (hereinafter referred to as "hydroxyl group-containing (meth)acrylate”). meth)acrylate.
• hydroxyl group-containing (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalate, and glycerol mono(meth)acrylate.
• acrylate, 2-hydroxy-3-phenoxypropyl acrylate, pentaerythritol tri(meth)acrylate, etc. preferably 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate. be.
• the polycarbodiimide compound according to the present invention has the polycarbodiimide (a), the polymer (b), and a (meth)acryloyl group and does not react with an isocyanate group within a range that does not impair the effects of the present invention. It may also be a reaction product of the compound (c) having a functional group to be obtained and other components. However, from the viewpoint of achieving the effects of the present invention, the polycarbodiimide (a), the polymer (b), and a compound (c) having a (meth)acryloyl group and a functional group capable of reacting with an isocyanate group. Preferably, only three types of reaction products are used.
• Other components include compounds with functional groups that can react with isocyanate groups, such as butanol such as 1-butanol, compounds with hydroxyl groups such as ethylene glycol and propylene glycol, and compounds with amino groups such as butylamine and cyclohexylamine.
• Examples include compounds having a carboxy group such as propionic acid, butanoic acid, and the like.
• the amount of the polycarbodiimide (a) in the total amount of raw material components of the polycarbodiimide compound is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 80% by mass. %, even more preferably 40 to 80% by weight, even more preferably 45 to 75% by weight.
• the blending amount is in the range of 10 to 90% by mass, the carbodiimide groups can be uniformly distributed in the cured product, and the carbodiimide groups can react with water molecules that have entered the cured product, thereby suppressing damage.
• the amount of the polymer (b) in the total amount of raw material components of the polycarbodiimide compound is preferably 5 to 80% by mass, more preferably 15 to 75% by mass, and even more preferably 18 to 70% by mass. %, even more preferably from 18 to 58% by weight, even more preferably from 22 to 50% by weight.
• the blending amount is in the range of 5 to 80% by mass, the carbodiimide groups can be uniformly distributed in the cured product, and the carbodiimide groups can react with water molecules that have entered the cured product, thereby suppressing damage.
• the amount of the compound (c) in the total amount of raw material components of the polycarbodiimide compound is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and even more preferably 4 to 10% by mass. It is. Within this range, since it can react with the resin (D) having a (meth)acryloyl group, the carbodiimide group can be uniformly distributed in the cured product, and water resistance is improved.
• the blending amount of the polymer (b) and the blending amount of the compound (c) in the total amount of raw material components of the polycarbodiimide compound are preferably such that the polymer (b) is 5 to 80% by mass and the compound (c) is 5 to 80% by mass.
• the carbodiimide groups can be uniformly distributed in the cured product, and the carbodiimide groups can react with water molecules that have entered the cured product, thereby suppressing damage.
• the amount of the polymer (b) to be blended with respect to 100 parts by mass of polycarbodiimide (a) is preferably 10 to 300 parts by mass, more preferably 20 to 140 parts by mass, and even more preferably 30 to 110 parts by mass. be.
• the amount of the polymer (b) is 10 parts by mass or more, the carbodiimide groups can be uniformly distributed in the cured product, so the carbodiimide groups react with water molecules that have entered the cured product, causing damage. You can suppress things.
• the blending amount of the polymer (b) is 300 parts by mass or less, the amount of carbodiimide groups in the cured product is small, and damage caused by water molecules that have penetrated into the cured product can be suppressed.
• the compounding amount of the compound (c) relative to 100 parts by mass of polycarbodiimide (a) is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 25 parts by mass. .
• the amount of compound (c) is 1 part by mass or more, it can react with the resin (D) having a (meth)acryloyl group, so that carbodiimide groups can be uniformly distributed in the cured product, Improves water resistance.
• the compounding amount of compound (c) is 50 parts by mass or less, the cured product has high strength and is easy to handle.
• the amount of the polymer (b) blended is preferably greater than the amount of the compound (c) blended.
• the carbodiimide groups cannot be uniformly distributed in the cured product, and the carbodiimide groups react with water molecules that have entered the cured product, suppressing damage. I can't.
• the blending amount of the polymer (b) per 1 mol part of polycarbodiimide (a) is preferably 0.1 to 2.0 mol parts, more preferably 0.2 to 1.0 mol parts, and even more preferably It is 0.4 to 0.6 mole part.
• the blending amount is in the range of 0.1 to 2.0 mole parts, the carbodiimide groups can be uniformly distributed in the cured product, and the carbodiimide groups can react with water molecules that have entered the cured product, thereby suppressing damage. .
• the compounding amount of the compound (c) per 1 mol part of polycarbodiimide (a) is preferably 0.1 to 2.1 mol parts, more preferably 0.5 to 2.0 mol parts, and even more preferably 1 .0 to 1.2 mole parts. Within this range, since it can react with the resin (D) having a (meth)acryloyl group, the carbodiimide group can be uniformly distributed in the cured product, and water resistance is improved.
• the structure of the polycarbodiimide compound is not particularly limited as long as it has a structural unit derived from polycarbodiimide (a) and a structural unit derived from the polymer (b), but it may further have a structural unit derived from the compound (c). It is preferable to have a structural unit derived from polycarbodiimide (a), a structural unit derived from polymer (b), and a structural unit derived from compound (c) only.
• the total amount of structural units derived from polycarbodiimide (a), structural units derived from polymer (b), and structural units derived from compound (c) in the polycarbodiimide compound is preferably 80% by mass or more, and more Preferably it is 90% by mass or more, more preferably 95% by mass or more, and even more preferably 100% by mass.
• Examples of the structure of the polycarbodiimide compound include polycarbodiimide compounds represented by the following formula (1) or formula (2), and preferably the polycarbodiimide compound represented by formula (1).
• A is a residue obtained by removing the isocyanate groups at both ends from polycarbodiimide (a)
• B is a residue obtained by removing two functional groups that can react with isocyanate groups from the polymer (b)
• C is a residue obtained by removing one functional group that can react with an isocyanate group from compound (c)
• x is a bond formed between one isocyanate group of the polycarbodiimide (a) and one of the functional groups that can react with the isocyanate group of the polymer (b).
• y is a bond formed between one isocyanate group of the polycarbodiimide (a) and one of the functional groups capable of reacting with the isocyanate group of the compound (c).
• the NCN equivalent (chemical formula weight per mol of carbodiimide group) of the polycarbodiimide compound is preferably 200 to 1,000, more preferably 250 to 800, still more preferably 300 to 600, even more preferably 320 to 600.
• compatibilization with the resin (D) having a (meth)acryloyl group is easy, and carbodiimide groups derived from the polycarbodiimide compound are uniformly present in the cured product. Therefore, the carbodiimide group reacts with the water molecules that have entered the cured product, thereby producing an excellent effect of inhibiting the entered water molecules from deteriorating the cured product.
• the NCN equivalent can be calculated by the method described in Examples.
• the method for producing the polycarbodiimide compound is not particularly limited.
• a polycarbodiimide compound can be produced by blending polycarbodiimide (a), polymer (b), and optionally compound (c) at the above-mentioned mixing ratio, and heating and stirring. can.
• the polycarbodiimide compound is produced by heating the polycarbodiimide (a) in advance, adding the polymer (b) and the compound (c) to the heated polycarbodiimide (a), and heating and stirring. be able to.
• the heating temperature of polycarbodiimide (a) is preferably 90 to 120°C, more preferably 100 to 115°C, even more preferably 105 to 115°C.
• the heating temperature is preferably 80 to 120°C, more preferably 90 to 110°C, and The temperature is preferably 90 to 104°C, and the heating and stirring time is preferably 1 to 10 hours, more preferably 3 to 8 hours.
• the heating temperature is 80°C or higher, a reaction product can be rapidly produced, and when the heating temperature is 120°C or lower, polymerization of compound (c) can be prevented.
• a polycarbodiimide compound can be suitably produced by any of the following methods (1) to (6).
• (1) Polycarbodiimide (a) and polymer (b) are reacted at 120°C or lower.
• Polycarbodiimide (a), polymer (b), and compound (c) are reacted at 120°C or lower.
• (3) Polycarbodiimide (a) and polymer (b) are reacted in a solvent.
• Polycarbodiimide (a), polymer (b), and compound (c) are reacted in a solvent.
• Polycarbodiimide (a) and polymer (b) are reacted in a solvent at 120°C or lower.
• the reaction may be further carried out in the presence of a catalyst.
• the solvent is preferably a hydrocarbon solvent or a ketone solvent, and specific examples include toluene, xylene, cyclohexanone, diisobutyl ketone, methyl isobutyl ketone, and methyl. Normal pentyl ketone is preferred.
• the heating temperature is preferably 40 to 120°C, more preferably 45 to 95°C, when adding the polymer (b) and compound (c) to polycarbodiimide (a) and heating and stirring. °C, more preferably 45 to 85 °C, even more preferably 50 to 80 °C, and the heating and stirring time is preferably 1 to 36 hours, more preferably 5 to 24 hours.
• the catalyst is preferably a tertiary amine compound such as 1,4-diazabicyclo[2.2.2]octane or triethylenediamine; or an organometallic compound such as dibutyltin dilaurate or tetraoctyl titanate.
• a polycarbodiimide compound By using a catalyst, a polycarbodiimide compound can be produced at a lower heating and stirring temperature. By using a solvent, a polycarbodiimide compound can be produced at a lower heating and stirring temperature.
• the heating temperature is preferably 40 to 120°C, more preferably 45 to 95°C. °C, more preferably 45 to 85 °C, even more preferably 50 to 80 °C, and the heating and stirring time is preferably 1 to 36 hours, more preferably 5 to 24 hours.
• the resin composition according to the present invention is a resin composition containing a resin (D) having a (meth)acryloyl group and the above-mentioned polycarbodiimide compound.
• the polycarbodiimide compound has an excellent effect of improving the water resistance of the resin (D) having a (meth)acryloyl group.
• the reason is not certain, it is presumed to be as follows. That is, the moiety derived from the polymer (b) facilitates compatibilization with the resin (D) having a (meth)acryloyl group, thereby uniformly distributing the polycarbodiimide compound in the resin composition and its cured product. Can be done.
• the site derived from the compound (c) contributes to maintaining a uniform structure in which the polycarbodiimide compound and the resin (D) having a (meth)acryloyl group are made compatible even under high temperature and high humidity conditions. Furthermore, the carbodiimide groups derived from polycarbodiimide (a) react with water molecules that have entered the cured product, thereby preventing the entered water molecules from deteriorating the cured product.
• the resin (D) having a (meth)acryloyl group is preferably one that does not contain a hydrophilic group from the viewpoint of water resistance.
• examples include acrylic resin (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyphenylene ether (meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate.
• acrylate pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, more preferably acrylic resin (meth)acrylate, epoxy( meth)acrylate, polyphenylene ether (meth)acrylate.
• the resin (D) preferably has a methacryloyl group.
• the weight average molecular weight of the resin (D) is preferably 40 to 1,000,000, more preferably 200 to 10,000, and even more preferably 1000 to 5,000.
• weight average molecular weight is 40 or more, pinholes due to volatilization during heat curing can be suppressed, and when it is 1,000,000 or less, moldability and handleability are excellent.
• the number of (meth)acryloyl groups per molecule of the resin (D) is preferably 1 to 1,000, more preferably 1 to 10, and even more preferably is from 1 to 5, more preferably from 2.
• radical polymerization initiator (E) examples include dialkyl monoperoxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butylcumyl peroxide; 2,5-dimethyl-2,5-di(t-butyl peroxide); ) hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, bis(t-butyldioxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3 , 5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate; diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide; t- Monoacylalky
• the resin composition may contain a crosslinking aid.
• a crosslinking aid known crosslinking aids can be used, such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, triallyl trimellitate, triallyl 1,2,4-benzenetricarboxylate.
• the resin composition according to the present invention may contain other components within a range that does not impede the effects of the present invention.
• Other components include resins such as epoxy resins, acrylic resins, urethane resins, and phenol resins; inorganic fillers such as silica; and solvents such as toluene and cyclohexanone.
• the content of the resin (D) in the solid content of the resin composition according to the present invention is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass. Mass%. When the content is 20 to 95% by mass, the cured product of the resin composition will have excellent water resistance.
• the content of the polycarbodiimide compound in the solid content of the resin composition according to the present invention is preferably 0.1 to 75% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 75% by mass. It is 15% by mass. When the content is 0.1 to 75% by mass, the cured product of the resin composition will have excellent water resistance.
• the content of the radical polymerization initiator (E) in the solid content of the resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. % by mass, more preferably 1 to 4% by mass.
• the content of the crosslinking aid in the solid content of the resin composition is preferably 0.1 to 40% by mass, more preferably 0.5 to 10% by mass, and still more preferably 2 to 40% by mass. It is 8% by mass.
• the solid content concentration in the total amount of the resin composition according to the present invention is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass. Note that the solid content refers to components excluding the solvent, and the solid content concentration in the total amount of the resin composition refers to the concentration of components excluding the solvent (ie, solid content) in the total amount of the resin composition.
• the method for producing the resin composition is not particularly limited.
• a polycarbodiimide compound, a resin (D) having a (meth)acryloyl group, and, if necessary, a radical polymerization initiator (E), a crosslinking aid, and other components are blended to have the above-mentioned contents. It can be produced by adding and stirring.
• the stirring temperature is preferably 10 to 100°C, more preferably 15 to 80°C, even more preferably 15 to 50°C.
• the stirring time is preferably 0.5 to 48 hours, more preferably 1 to 48 hours, even more preferably 1 to 24 hours, even more preferably 1 to 12 hours.
• the cured resin product according to the present invention is a cured product of the resin composition according to the present invention. Details of the resin composition are as described above.
• the heating temperature during heating can be appropriately selected depending on the composition of the resin composition, but is preferably 100 to 250°C, more preferably 150 to 250°C, still more preferably 170 to 220°C, and even more preferably is 180-200°C.
• the heating time can also be appropriately selected depending on the composition of the resin composition, but is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, even more preferably 2 to 10 hours, even more preferably 4 hours. ⁇ 7 hours.
• a toluene solution of di-n-butylamine of a known concentration is mixed with the isocyanate-terminated polycarbodiimide obtained by the carbodiimidization reaction, and the terminal isocyanate group and di-n-butylamine are reacted, and the remaining Di-n-butylamine was neutralized and titrated with a standard hydrochloric acid solution, and the remaining amount of isocyanate groups (terminal NCO amount [mass %]) was calculated.
• the degree of polymerization of the carbodiimide group was determined from the amount of terminal NCO.
• Example 1-1 39.0g of the isocyanate-terminated polycarbodiimide (a1-1) obtained in Synthesis Example 1-1 was placed in a separate 0.3L container equipped with a reflux tube and a stirrer, heated to 110°C, and the polymer (b ), 55.8 g of G3000 (0.5 mol per 1 mol of isocyanate-terminated polycarbodiimide), and 4.6 g of 4-HBA (1.1 mol per 1 mol of isocyanate-terminated polycarbodiimide) as compound (c). was added and reacted for 5 hours while heating and stirring at 100°C to obtain a reaction product.
• the polymer (b ) 55.8 g of G3000 (0.5 mol per 1 mol of isocyanate-terminated polycarbodiimide), and 4.6 g of 4-HBA (1.1 mol per 1 mol of isocyanate-terminated polycarbodiimide) as compound (c).
• the theoretical molecular weight can be determined from the hydroxyl value.
• the polycarbodiimide compound, a polyphenylene ether type methacrylate (manufactured by Sabic, trade name "PPE SA9000", weight average molecular weight 1700, methacryloyl group per molecule of resin) as the resin (D) having (meth)acryloyl groups.
• Example 1-1 except that the types, blending amounts, and manufacturing conditions of polycarbodiimide (a), polymer (b), compound (c), and compound (c') were as shown in Tables 2 to 7.
• a polycarbodiimide compound was obtained by performing the same operation as above.
• the polycarbodiimide compound and the components shown in Tables 2 to 7 were blended in the amounts shown in Tables 2 to 7, and the resin compositions were obtained by stirring and mixing under the manufacturing conditions shown in Tables 2 to 7. .
• this polycarbodiimide compound Since the mol ratio between the structure and the structure derived from compound (c) is 8:1:2, this polycarbodiimide compound has 2 mol of polycarbodiimide (a) with a theoretical degree of polymerization of 3.0 in one molecule. The number of carbodiimide groups in one molecule of the polycarbodiimide compound is: 6).
• the polycarbodiimide compound and the components shown in Table 6 were blended in the amounts shown in Table 6, and the mixture was stirred and mixed under the manufacturing conditions shown in Table 6 to obtain a resin composition.
• Example 6-1 64.0 g of the isocyanate-terminated polycarbodiimide (a1-4) obtained in Synthesis Example 1-4 was placed in a separate 0.3 L container equipped with a reflux tube and a stirrer, and 100 g of cyclohexanone as a solvent was added thereto at 50°C. After heating to a temperature of 100 ml and confirming that it became uniform visually, 30.1 g of G1000 as polymer (b) (0.5 mol per 1 mol of isocyanate-terminated polycarbodiimide) and compound (c) were added.
• Examples 6-2 to 6-12 The same operation as in Example 6-1 except that the types, blending amounts, and manufacturing conditions of polycarbodiimide (a), polymer (b), compound (c), solvent, and catalyst were as shown in Table 8. A polycarbodiimide compound was obtained. Next, the polycarbodiimide compound and the components shown in Table 8 were blended in the amounts shown in Table 8, and the resin compositions were obtained by stirring and mixing under the manufacturing conditions shown in Table 8.
• the resin compositions according to each example had a moist heat test result of 3 or more, and had excellent water resistance.
• the polycarbodiimide compound did not have a structure derived from the polymer (b), so the moist heat test result was 1, and the water resistance was poor.
• the resin composition according to Comparative Example 1-3 contained a monocarbodiimide compound instead of a polycarbodiimide compound, the result of the moist heat test was 1, and the water resistance was poor.
• the diisocyanate constituting the polycarbodiimide compound was an aromatic diisocyanate, so the result of the moist heat test was 1, and the water resistance was poor.
• the diisocyanate constituting the polycarbodiimide compound was an aromatic diisocyanate, so the result of the moist heat test was 1, and the water resistance was poor.
• polycarbodiimide compounds are produced by reacting polycarbodiimide (a), polymer (b), and compound (c) in the presence of a solvent and a catalyst, heating is not necessary. Although the reaction was carried out at a relatively low temperature and stirring temperature of 50 to 80°C, a polycarbodiimide compound could be produced satisfactorily. Moreover, the obtained resin composition had excellent resin water resistance.

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