CN102574979A - Acrylic modified urethane urea resin composition and molded article obtained using same - Google Patents

Acrylic modified urethane urea resin composition and molded article obtained using same Download PDF

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Publication number
CN102574979A
CN102574979A CN201080040151XA CN201080040151A CN102574979A CN 102574979 A CN102574979 A CN 102574979A CN 201080040151X A CN201080040151X A CN 201080040151XA CN 201080040151 A CN201080040151 A CN 201080040151A CN 102574979 A CN102574979 A CN 102574979A
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urea resin
type structure
ring type
acid modified
acrylic acid
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CN102574979B (en
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田中浩二郎
今中正能
山本辰弥
菅谷英史
小尾一树
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • 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
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/67—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
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • 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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/83—Chemically modified polymers
    • 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

Abstract

Disclosed is an acrylic modified urethane urea resin composition which is characterized by containing an acrylic modified urethane urea resin (1) and a solvent (2), said acrylic modified urethane urea resin (1) being obtained by reacting an alicyclic structure-containing polyol (A), an alicyclic structure-containing polyisocyanate (B), an alicyclic structure-containing polyamine (C) and an acrylic compound (D) having an active hydrogen atom-containing group. Also disclosed is a molded article which is obtained using the acrylic modified urethane urea resin composition. The resin composition is capable of forming a molded article that has a good balance between heat resistance and solvent resistance at such an excellent level that dissolution, deformation, discoloration or the like of the surface of the molded article does not occur even in cases when various solvents adhere to the surface.

Description

Acrylic acid modified carbamate urea resin compsn and the molding that uses it to obtain
Technical field
The present invention relates to and with for example formed material, coating agent, tackiness agent to be the acrylic acid modified carbamate urea resin compsn that uses in the various uses of representative.
Background technology
The molding that uses the polyurethane series formed material to obtain uses in the various uses such as skin material that constitute trolley part and household electrical appliances parts, wrapping material, leather-like sheet now.
For above-mentioned molding, require the various characteristics of its application purpose of reply.Under the situation about for example in the car interior-exterior package material, using; Sometimes require not cause by alcohol resistance, the oil resistant of the degree of the distortion on the molding surface of adhering to generation of the grease in alcohol, the food etc., variable color etc. acid; In addition; Under long-time situation about exposing under the hot environment in summer, require not cause the thermotolerance of degree of the distortion etc. of molding sometimes.
As the formed material that is difficult to cause above-mentioned distortion that results from alcohol etc. etc.; Known for example by make gather carbonic acid tetramethylene esterdiol and more than a kind or 2 kinds organic diisocyanate reaction and the specific prepolymer that obtains with have the chain extension agent of 2 abilities and form with the active hydrogen of the isocyanate reaction of this prepolymer; To have carried out terminal terminated, molecular weight 3～200,000 and gel % be thermoplastic polyurethane formed material (reference example such as patent documentation 1 below 5% to mol ratio through above-mentioned prepolymer/chain extension agent in order to surpass 1 value, to use the reaction terminating material with 1 ability and unreacting isocyanate reactive activity hydrogen of the end of above-mentioned prepolymer.)。
But, the molding that uses above-mentioned thermoplastic polyurethane formed material to obtain, aspect thermotolerance, not enough in practicality sometimes, long-term exposure causes distortion etc. sometimes under the situation under the hot environment.
On the other hand, when above-mentioned molding is fixed in the prescribed position of various goods, usually, use tackiness agent more.When for example making trolley part, household electrical appliances parts, sometimes the organic solvent type tackiness agent is used to have bonding between the member that the molding of the shape of regulation constitutes.
But contained organic solvent in the above-mentioned tackiness agent is invaded the surface of polyurethane series molding sometimes, causes the dissolving, distortion, variable color on this molding surface etc.
Will membranaceous or flaky above-mentioned molding when special with an organic solvent under range upon range of etc. the situation of type tackiness agent, owing to the influence of organic solvent contained in the above-mentioned tackiness agent, cause the distortion and the variable colors such as dissolving, contraction of film etc. sometimes.
Like this, industrial community requires a kind of formed material that can form following molding of exploitation, even this molding possesses the solvent resistance and the above-mentioned thermotolerance of the degree that under above-mentioned situation, does not also cause the surperficial dissolving of molding, distortion, variable color etc.
But; The molding that uses in the above-mentioned patent documentation 1 the above-mentioned thermoplastic polyurethane formed material of record to obtain; Though have good patience for lubricant components such as alcohol, oleic acid; But the various organic solvents for the strong solvent being representative possess enough solvent resistances hardly, and the resin that still is difficult to sometimes prevent adhering to of above-mentioned solvent to cause is from the surperficial distortion of dissolving, the molding on molding surface, variable color etc.
As previously discussed, though pressing for a kind of can formation, industrial community has excellent thermotolerance concurrently and for the formed material of the molding of the solvent resistance of the excellence of organic solvent, practical situation are not find as yet.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 7-41540 communique
Summary of the invention
The problem that invention will solve
The problem that the present invention will solve is to provide the resin combination that can form following molding, even this molding has the solvent resistance and the thermotolerance of excellence of the degree of the dissolving that also do not cause the molding surface under the situation that all kinds of SOLVENTS adheres to, distortion, variable color etc. concurrently.
Be used to solve the means of problem
The inventor etc. are in the process that solves above-mentioned problem and study, and have studied the technical scheme that imports aliphatics ring type structure in the urethane resin of record in above-mentioned document 1.Particularly, study the combination of various polyvalent alcohols, POLYMETHYLENE POLYPHENYLISOCYANATE, but also studied the combination with various chain extension agents.
Its result finds; So long as contain under the situation of acrylic acid modified carbamate urea resin compsn of the acrylic acid modified carbamate urea resin that makes the polyvalent alcohol, the POLYMETHYLENE POLYPHENYLISOCYANATE that contains aliphatics ring type structure that contain aliphatics ring type structure, contain the polyamines of aliphatics ring type structure and have the acrylic compounds reaction of the group that contains active hydrogen atom and obtain and solvent, just can form the solvent resistance and the stable on heating molding that have excellence concurrently.
Promptly; The present invention relates to acrylic acid modified carbamate urea resin compsn and the molding that has used said composition to form; Said compsn is characterised in that; Contain acrylic acid modified carbamate urea resin (1) and solvent (2), this acrylic acid modified carbamate urea resin (1) obtains through acrylic compounds (D) reaction that makes the polyvalent alcohol (A) that contains aliphatics ring type structure, the POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure, the polyamines (C) that contains aliphatics ring type structure and have the group that contains active hydrogen atom.
The effect of invention
So long as acrylic acid modified carbamate urea resin compsn of the present invention; Just can form and possess excellent solvent resistance and stable on heating molding, therefore can in the manufacturing of the skin material of for example trolley part, household electrical appliances parts, wrapping material, film, sheet material, leather-like sheet etc., use.
In addition, acrylic acid modified carbamate urea resin compsn of the present invention possesses excellent solvent resistance and stable on heating tunicle etc. owing to can form, therefore can use in the surface coated agent of for example various base materials, tackiness agent etc.
Embodiment
At first, the acrylic acid modified carbamate urea resin (1) that uses among the present invention is described.
The acrylic acid modified carbamate urea resin (1) that uses among the present invention obtains through acrylic compounds (D) reaction that makes polyvalent alcohol (A) that contains aliphatics ring type structure and the POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure and the polyamines (C) that contains aliphatics ring type structure and have the group that contains active hydrogen atom.
Aforesaid propylene acid modified amido manthanoate urea resin (1), on the solvent resistance and thermotolerance of performance excellence, it is necessary having aliphatics ring type structure.Above-mentioned aliphatics ring type structure all is important by each supply of the above-mentioned polyvalent alcohol that contains aliphatics ring type structure and POLYMETHYLENE POLYPHENYLISOCYANATE that contains aliphatics ring type structure and the polyamines that contains aliphatics ring type structure.For example; Even the mass ratio of the aliphatics ring type structure that exists in the aforesaid propylene acid modified amido manthanoate urea resin (1) is an equal extent; But replacement contains the POLYMETHYLENE POLYPHENYLISOCYANATE of aliphatics ring type structure and has used in the resin combination of aliphatic polyisocyante, can not form the molding that possesses required solvent resistance sometimes.
As aforesaid propylene acid modified amido manthanoate urea resin (1), from obtaining having concurrently the excellent solvent resistance and the viewpoint of stable on heating molding, the preferred material that uses the aliphatics ring type structure of scope with 20～60 quality %.Need to prove; The mass ratio of above-mentioned aliphatics ring type structure; Be meant with respect to the polyvalent alcohol that contains aliphatics ring type structure (A) of the raw material that uses in the manufacturing as aforesaid propylene acid modified amido manthanoate urea resin (1) and contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and have the total quality of the acrylic compounds (D) of the group that contains active hydrogen atom, the quality of aliphatics ring type structure shared ratio in above-mentioned raw materials.
Aforesaid propylene acid modified amido manthanoate urea resin (1) has amino-formate bond and urea key.Use under the situation of the so-called urethane acrylate that does not have the urea key, forming process property is low sometimes, is difficult to make the for example molding such as film of thin-walled property.Therefore; As aforesaid propylene acid modified amido manthanoate urea resin (1); From the forming process property of excellence, the viewpoint that has good thermotolerance and solvent resistance simultaneously concurrently is set out, the preferred acrylic acid modified carbamate urea resin that uses the urea key with 4～10 quality %; This ratio is 5～8 quality % more preferably, are preferably 6～7 quality % especially.Need to prove; The mass ratio of above-mentioned urea key; Be meant with respect to the raw material that uses in the manufacturing as aforesaid propylene acid modified amido manthanoate urea resin (1) above-mentioned and contain the polyvalent alcohol (A) of aliphatics ring type structure and contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and have the total quality of the acrylic compounds (D) of the group that contains active hydrogen atom, the quality of urea bond structure shared ratio in above-mentioned raw materials.
In addition; As aforesaid propylene acid modified amido manthanoate urea resin (1); Forming process property from excellence; The viewpoint that has good thermotolerance and solvent resistance simultaneously concurrently is set out, the preferred acrylic acid modified carbamate urea resin that uses amino-formate bond with 5～15 quality %, and this ratio is 7～9 quality % more preferably.Need to prove; The mass ratio of above-mentioned amino-formate bond; Be meant with respect to the raw material that uses in the manufacturing as aforesaid propylene acid modified amido manthanoate urea resin (1) above-mentioned and contain the polyvalent alcohol (A) of aliphatics ring type structure and contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and have the total quality of the acrylic compounds (D) of the group that contains active hydrogen atom, the quality of carbamate bond structure shared ratio in above-mentioned raw materials.
As aforesaid propylene acid modified amido manthanoate urea resin (1); In the solvent resistance and the stable on heating while of excellence; Keep good forming process property aspect; The preferred acrylic acid modified carbamate urea resin with weight-average molecular weight of 5000～200000, more preferably 15000～200000 the scope used.Need to prove that the weight-average molecular weight of aforesaid propylene acid modified amido manthanoate urea resin (1) is to use gel permeation chromatography (GPC), use THF as elutriant, the value that adopts vinylbenzene to convert and obtain.
The acrylic acid modified carbamate urea resin (1) that uses among the present invention; From having excellent solvent resistance and thermotolerance aspect concurrently; Preferred to use equivalent weight from the acryl of aforesaid propylene acid compounds (D) be the acrylic acid modified carbamate urea resin of 10000～50000 scope, this value more preferably 10000～30000.Need to prove; The equivalent weight of so-called aforesaid propylene acyl group is meant with the polyvalent alcohol that contains aliphatics ring type structure (A) that constitutes aforesaid propylene acid modified amido manthanoate urea resin (1) and the total quality of acrylic compounds (D) that contains the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and have a group that contains active hydrogen atom divided by the value from the equivalent gained of the acryl of aforesaid propylene acid compounds (D) that exists in the sour modified amido manthanoate of the aforesaid propylene urea resin.
Next, the polyvalent alcohol that contains aliphatics ring type structure (A) that uses in the manufacturing to aforesaid propylene acid modified amido manthanoate urea resin (1) describes.
As the polyvalent alcohol that contains aliphatics ring type structure (A) that uses among the present invention, preferably using OH value is the material of the scope of 30～230mgKOH/g, more preferably is used for the material of the scope of 50～230mgKOH/g.Need to prove that the OH value of above-mentioned polyvalent alcohol (A) is the value of measuring according to JIS K0070.
As the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure; Can use polycarbonate polyol, the polyester polyol that contains aliphatics ring type structure, the polyether glycol that contains aliphatics ring type structure that for example contain aliphatics ring type structure, contain the acrylic acid series multiple alcohol of aliphatics ring type structure etc., the preferred glycol that contains aliphatics ring type structure that uses.In addition; In these; From having excellent solvent resistance and stable on heating viewpoint concurrently; More preferably use polycarbonate polyol that contains aliphatics ring type structure and the polyester polyol that contains aliphatics ring type structure, preferred especially polycarbonate diol that contains aliphatics ring type structure and the polyester glycol that contains aliphatics ring type structure of using.
As the above-mentioned polycarbonate polyol that contains aliphatics ring type structure, can use for example make carbonic ether and/or phosgene and after the polyvalent alcohol that contains aliphatics ring type structure (a1) reaction and the product that obtains of about lower molecular weight of about 50～400 of stating.
As above-mentioned carbonic ether, can use for example methyl carbonate, methylcarbonate, ethyl-carbonate, diethyl carbonate, cyclic carbonate ester, diphenyl carbonate etc.
As can with the polyvalent alcohol that contains aliphatics ring type structure (a1) of above-mentioned carbonic ether, phosgene reaction, for example can use 1,2-cyclobutanediol, 1,3-encircles pentanediol, 1,4-cyclohexanediol, ring heptanediol, ring ethohexadiol, 1; 4-cyclohexanedimethanol, hydroxypropyl hexalin, three rings [5,2,1,0,2; 6] decane-dimethanol, dicyclo [4,3,0]-nonane glycol, two cyclohexanediols, three rings [5,3,1; 1] dodecanediol, dicyclo [4,3,0] nonane dimethanol, three rings [5,3,1; 1] dodecyl-di-alcohol, hydroxypropyl three ring [5,3,1,1] dodecanols, spiral shell [3,4] ethohexadiol, butyl cyclohexanediol, 1; 1 '-bicyclohexylidene base glycol, phloroglucitol, Hydrogenated Bisphenol A 99,1,3-diamantane glycol etc. wherein preferably use 1,4 cyclohexane dimethanol.
As the above-mentioned polyester polyol that contains aliphatics ring type structure, can use the reaction of the polyvalent alcohol that contains aliphatics ring type structure that for example makes about lower molecular weight of about 50～400 and polycarboxylic acid and the product that obtains or make low molecular polylol and contain the polycarboxylic acid reaction of aliphatics ring type structure and cyclic ester compounds such as the part of the product that obtains or above-mentioned product and 6-caprolactone, γ-Wu Neizhi carry out ring-opening polymerization and the product of addition etc.
As the polyvalent alcohol that contains aliphatics ring type structure that in the manufacturing of the above-mentioned polyester polyol that contains aliphatics ring type structure, can use, can use with as the illustrative same polyvalent alcohol that contains aliphatics ring type structure of polyvalent alcohol (a1) that contains aliphatics ring type structure of the polyvalent alcohol that contains aliphatics ring type structure that in the manufacturing of the above-mentioned polycarbonate polyol that contains aliphatics ring type structure, uses.
In addition; As can with the above-mentioned low-molecular-weight polycarboxylic acid that contains the polyol reaction of aliphatics ring type structure; Can be with the aliphatics polycarboxylic acid, 1 of for example succsinic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, dimeracid; 4-cyclohexane cyclohexanedimethanodibasic, hexanaphthene tricarboxylic acid etc. contain polycarboxylic acid, phthalic acid, m-phthalic acid, the terephthalic acid, 1 of aliphatics ring type structure; 4-naphthalic acid, 2; 3-naphthalic acid, 2, aromatic series polycarboxylic acid such as 6-naphthalic acid, biphenyl dicarboxylic acid, trimellitic acid, PMA and these acid anhydrides or ester derivative preferably use the aliphatics polycarboxylic acid separately or more than 2 kinds and usefulness.
The polycarboxylic acid that contains aliphatics ring type structure as in the manufacturing of the above-mentioned polyester polyol that contains aliphatics ring type structure, using with likewise above-mentioned, can use 1,4 cyclohexanedicarboxylic acid etc.
As with the reaction of the above-mentioned polycarboxylic acid that contains aliphatics ring type structure in the polyvalent alcohol that can use, except the above-mentioned polyvalent alcohol (a1) that contains aliphatics ring type structure, can also use for example terepthaloyl moietie, glycol ether, triglycol, Tetraglycol 99,1,2-Ucar 35,1; Ammediol, DPG, tripropylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2; 3-butyleneglycol, 1,5-pentanediol, 1,5-pinakon, 1,6-pinakon, 2; 5-pinakon, 1,7-heptanediol, 1,8-ethohexadiol, 1; 9-nonanediol, decamethylene-glycol, 1,11-undecane glycol, 1; 12-dodecanediol, 2-methyl isophthalic acid, ammediol, NSC 6366,2-butyl-2-ethyl-1, ammediol, 3-methyl isophthalic acid; 5-pentanediol, 2-ethyl-1,3-pinakon, 2-methyl isophthalic acid, 8-ethohexadiol, glycerine, TriMethylolPropane(TMP), one two (TriMethylolPropane(TMP)s), two aliphatic polyols such as three (TriMethylolPropane(TMP)s), tetramethylolmethane etc. that contract that contract.
As the above-mentioned polyether glycol that contains aliphatics ring type structure, for example can use to be initiator the polyether glycol that the oxyalkylene addition polymerization is obtained with the compound more than a kind or 2 kinds with 2 above active hydrogen atoms.
As above-mentioned initiator, can use for example Hydrogenated Bisphenol A 99, A Hydrogenated Bisphenol A F, 1,4 cyclohexane dimethanol etc. and so on and the above-mentioned same initiator of the polyvalent alcohol that contains aliphatics ring type structure (a1).In addition; As required, also can be with present known terepthaloyl moietie, glycol ether, triglycol, Ucar 35, trimethylene, 1,3 butylene glycol, 1; 4-butyleneglycol, 1, aliphatic polyols such as 6-pinakon, NSC 6366, glycerine, trimethylolethane, TriMethylolPropane(TMP) are also used.
As above-mentioned oxyalkylene, can use for example ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min., Epicholorohydrin, THF etc.
As the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure; Owing to can form the molding of solvent resistance, thermotolerance, excellent in te pins of durability, therefore preferably with the above-mentioned polycarbonate polyol that contains aliphatics ring type structure, contain the polyester polyol of aliphatics ring type structure or contain other the chain extension agent that contains active hydrogen of combinations such as polyether glycol use of aliphatics ring type structure.
As above-mentioned other the chain extension agent that contains active hydrogen, can be with for example terepthaloyl moietie, 1,2-Ucar 35,1; 3-butyleneglycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 3-methyl isophthalic acid; 5-pentanediol, 1,6-pinakon, 3,3 '-dihydroxymethyl heptane, 1; 4-cyclohexanedimethanol, NSC 6366,3, independent or combination uses more than 2 kinds such as polyvalent alcohol such as two (hydroxymethyl) heptane of 3-, glycol ether, DPG, glycerine, TriMethylolPropane(TMP), sorbyl alcohol, quinhydrones two (hydroxyethyl) ether.
Among the present invention; Except the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure, can other polyvalent alcohols combinations such as known aliphatic polycarbonate polybasic alcohol, aromatic copolycarbonate polyvalent alcohol, aliphatic polyester polyols, aromatic polyester polyol, aliphatic poly ethoxylated polyhydric alcohol, aromatic polyether polyvalent alcohol in the past be used as required.
The above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure; Preferably with respect to the polyvalent alcohol that contains aliphatics ring type structure (A) of the raw material that uses in the manufacturing as acrylic acid modified carbamate urea resin of the present invention (1) with contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and the total quality of acrylic compounds (D), in the scope of 40～80 quality %, use.
Below, the above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure is described.
As the above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure; Can use for example isophorone diisocyanate, 4; 4 '-dicyclohexyl methane diisocyanate, 2; 4-and/or 2,6-methylcyclohexane diisocyanate, cyclohexylidene vulcabond, methyl cyclohexylidene vulcabond, two (2-ethyl isocyanate base)-4-cyclohexylidene-1,2-dicarboxylic acid esters and 2; 5-and/or 2,6-norbornene alkyl diisocyanate, dimer acid diisocyanate, norbornane triisocyanate etc.Wherein, from giving molding of the present invention excellent solvent resistance and stable on heating viewpoint, preferably use vulcabond; More preferably use isophorone diisocyanate, 4; 4 '-dicyclohexyl methane diisocyanate especially preferably uses 4,4 '-dicyclohexyl methane diisocyanate.
In addition; Among the present invention; Except the above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure, can other POLYMETHYLENE POLYPHENYLISOCYANATE combination such as aliphatic polyisocyantes such as aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate be used as required.
The above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure; With respect to the polyvalent alcohol that contains aliphatics ring type structure (A) of the raw material that uses in the manufacturing as the acrylic acid modified carbamate urea resin (1) that obtains with contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and the total quality of acrylic compounds (D), preferably in the scope of 15～50 quality %, use.
Next, the above-mentioned polyamines (C) that contains aliphatics ring type structure is described.
The above-mentioned polyamines (C) that contains aliphatics ring type structure is used for the urea key is imported aforesaid propylene acid modified amido manthanoate urea resin.
As the above-mentioned polyamines (C) that contains aliphatics ring type structure; Can use for example isophorone diamine, 4; 4 '-dicyclohexyl methyl hydride diamines, DACH, methyl DACH, piperazine, norbornylene diamines etc. wherein from forming the viewpoint of the excellent molding of excellent heat resistance and solvent resistance, preferably use diamines; Especially preferably use isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines.
In addition, among the present invention, except the above-mentioned polyamines (C) that contains aliphatics ring type structure, as required, can be in the scope of not damaging effect of the present invention with in the past quadrol etc. as chain extension agent and known aliphatic polyamine etc. and using.
The above-mentioned polyamines (C) that contains aliphatics ring type structure; With respect to the polyvalent alcohol that contains aliphatics ring type structure (A) of the raw material that uses in the manufacturing as the acrylic acid modified carbamate urea resin (1) that obtains with contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and the total quality of acrylic compounds (D), preferably in the scope of 1～20 quality %, use.
Next, above-mentioned acrylic compounds (D) with the group that contains active hydrogen atom is described.
The acrylic compounds of using among the present invention with the group that contains active hydrogen atom (D); Be used for acryl is imported aforesaid propylene acid modified amido manthanoate urea resin, use have can with the material of the group that contains active hydrogen atom of isocyanic ester radical reaction.
As the above-mentioned group that contains active hydrogen atom, can enumerate for example hydroxyl, carboxyl etc., be preferably hydroxyl.
As aforesaid propylene acid compounds (D), can use the acrylic compounds with above-mentioned hydroxyl, acrylic compounds etc. with carboxyl, the preferred use has the acrylic compounds of hydroxyl.
As acrylic compounds, for example can use (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester etc. to contain alkyl acrylate, polyoxyethylene glycol mono acrylic ester, W 166 mono acrylic ester of hydroxyl etc. with above-mentioned hydroxyl.Wherein, from solvent resistance and stable on heating viewpoint, the preferred alkyl acrylate that contains hydroxyl that uses, the viewpoint of the easy property that obtains from raw material is preferably used vinylformic acid 2-hydroxy methacrylate, vinylformic acid 4-hydroxyl butyl ester.
Aforesaid propylene acid compounds (D); With respect to the polyvalent alcohol that contains aliphatics ring type structure (A) of the raw material that uses in the manufacturing as acrylic acid modified carbamate urea resin (1) with contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and the total quality of acrylic compounds (D), preferably in the scope of 0.05～10 quality %, use.
In addition, the part of aforesaid propylene acid compounds (D) in acrylic acid modified carbamate urea resin compsn of the present invention, can exist with unreacted state.That is, acrylic acid modified carbamate urea resin compsn of the present invention with aforesaid propylene acid modified amido manthanoate urea resin, can contain unreacted aforesaid propylene acid compounds (D).
Next, the solvent (2) that uses among the present invention is described.
As above-mentioned solvent (2), can be with an organic solvent and water solvent, but from can further improving the viewpoint of the formability of molding, more preferably with an organic solvent.
As above-mentioned solvent (2); Under the situation with an organic solvent; Do not have special qualification; Can use for example vinyl acetic monomer, N-BUTYL ACETATE, ethyl lactate, cellosolve, cellosolve acetate, acetone, methyl ethyl ketone, MIBK, pimelinketone, toluene, YLENE, N, N,N-DIMETHYLACETAMIDE, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, acetonitrile, DMSO 99.8MIN., N-Methyl pyrrolidone, N-ethyl pyrrolidone, methyl alcohol, Virahol, 2-butanols, propyl carbinol, Virahol, ethylene glycol monomethyl ether acetate etc., these can use separately or and use.In addition, these organic solvents can suitably be selected according to the purposes of using.
In addition; Mass ratio in the acrylic acid modified carbamate urea resin compsn of the present invention, aforesaid propylene acid modified amido manthanoate urea resin (1) and above-mentioned solvent (2); Be preferably (1)/(2)=10～50/90～50 more preferably 15～35/85～65.
Next, the method for manufacture to aforesaid propylene acid modified amido manthanoate urea resin (1) describes.
As the method for manufacture of aforesaid propylene acid modified amido manthanoate urea resin (1), can enumerate for example following method for making (i)～method for making method (ii).Wherein, since control reaction easily, the method manufacturing of (i) below preferred the employing.
Method for making (i) is following method: under above-mentioned solvent (2); Make the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure and above-mentioned contain the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure and as required above-mentioned other the chain extension agent reaction that contains active hydrogen and obtain having the carbamate prepolymer of NCO in molecular end; Next, through making above-mentioned carbamate prepolymer and above-mentioned polyamines (C) and aforesaid propylene acid compounds (D) reaction that contains aliphatics ring type structure make acrylic acid modified carbamate urea resin (1).
Above-mentioned polyvalent alcohol (A) and the above-mentioned reaction that contains the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure that contains aliphatics ring type structure; The equivalent ratio [NCO/hydroxyl] of the NCO that is preferably had at hydroxyl that this polyvalent alcohol (A) that contains aliphatics ring type structure is had and the POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure is carried out under the scope of 1.1/1.0～5.0/1.0, more preferably the scope of 1.5/1.0～3.0/1.0.In addition, above-mentioned polyvalent alcohol (A) and the above-mentioned reaction that contains the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure that contains aliphatics ring type structure preferably carried out under 20～120 ℃ the condition about about 30 minutes～24 hours.
Contain the polyvalent alcohol (A) of aliphatics ring type structure and contain carbamate prepolymer and the above-mentioned reaction that contains the polyamines (C) and the aforesaid propylene acid compounds (D) of aliphatics ring type structure that the reaction of the POLYMETHYLENE POLYPHENYLISOCYANATE (B) of aliphatics ring type structure obtains, have NCO in above-mentioned molecular end by above-mentioned; For example; Can be through disposable or supply with above-mentioned carbamate prepolymer one by one and above-mentionedly contain the polyamines (C) of aliphatics ring type structure and make its reaction; Thereby make the carbamate urea prepolymers; Again through make this carbamate urea prepolymers and aforesaid propylene acid compounds (D) reaction, thereby make acrylic acid modified carbamate urea resin (1).At this moment, the NCO that has of above-mentioned carbamate prepolymer and the equivalent ratio [amino/NCO] of the amino of the polyamines (C) that contains aliphatics ring type structure are preferably the scope of 0.70/1.0～0.99/1.0.In addition, also can make in about about 1～3 hour of reaction under 20～80 ℃ the condition through with above-mentioned carbamate prepolymer with above-mentionedly contain the polyamines (C) of aliphatics ring type structure and aforesaid propylene acid compounds (D) is disposable or mix one by one.
In addition; Above-mentioned method for making (ii) is following method: under above-mentioned solvent (2); Make above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) and above-mentioned polyamines (C) reaction that contains aliphatics ring type structure that contains aliphatics ring type structure; Thereby obtain having the polyureas prepolymer of NCO in molecular end; Next, make this polyureas prepolymer and above-mentioned contain polyvalent alcohol (A) and the aforesaid propylene acid compounds (D) of aliphatics ring type structure and above-mentioned other the chain extension agent reaction that contains active hydrogen as required, thereby make acrylic acid modified carbamate urea resin (1).
Above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) and the above-mentioned reaction that contains the polyamines (C) of aliphatics ring type structure that contains aliphatics ring type structure, the equivalent ratio [NCO/amino] of the amino that is preferably had at NCO that the above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure is had and the above-mentioned polyamines (C) that contains aliphatics ring type structure is carried out under the scope of 1.1/1.0～5.0/1.0.In addition, above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) and the above-mentioned reaction that contains the polyamines (C) of aliphatics ring type structure that contains aliphatics ring type structure preferably carried out under 20～80 ℃ the condition about about 30 minutes～1 hour.
The polyureas prepolymer and the above-mentioned reaction that contains the polyvalent alcohol (A) and the aforesaid propylene acid compounds (D) of aliphatics ring type structure that obtain by above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure and the above-mentioned reaction that contains the polyamines (C) of aliphatics ring type structure, have NCO in above-mentioned molecular end; For example; Can be through disposable or supply with above-mentioned polyureas prepolymer one by one and above-mentionedly contain the polyvalent alcohol (A) of aliphatics ring type structure and make its reaction; Thereby be manufactured on the carbamate urea prepolymers that molecular end has NCO; Through make this carbamate urea prepolymers and aforesaid propylene acid compounds (D) reaction, thereby make acrylic acid modified carbamate urea resin (1).In addition, polyvalent alcohol (A) that also can be through above-mentioned polyureas prepolymer and above-mentioned being contained aliphatics ring type structure and aforesaid propylene acid compounds (D) are disposable or mix one by one and its reaction is made.
When making aforesaid propylene acid modified amido manthanoate urea resin (1), under above-mentioned method for making (i) and the situation (ii), all can use tertiary amine catalyst, organo-metallic series catalysts to promote reaction as required.
Contain the acrylic acid modified carbamate urea resin (1) that obtains by above method and the of the present invention acrylic acid modified carbamate urea resin compsn of solvent (2), can contain solidifying agent, curing catalyst as required.
As above-mentioned solidifying agent, can use light curing agent, thermal curing agents such as for example ultraviolet curing agent, electrocuring agent.
Above-mentioned ultraviolet curing agent is a light sensitizing property material, can use the for example such benzoin ether system of benzoin alkylether; Benzophenone series such as UVNUL MS-40, methyl o-benzoyl yl benzoic acid ester; Benzyl dimethyl ketal, 2,2-diethoxy acetophenone, 2-hydroxy-2-methyl Propiophenone, 4-sec.-propyl-2-hydroxy-2-methyl Propiophenone, 1, methyl phenyl ketones such as 1-dichloroacetophenone system; Thioxanthone based compounds such as 2-clopenthixal ketone, 2-methyl thioxanthone, 2-isopropyl thioxanthone.
As above-mentioned electrocuring agent, can use for example haloalkyl benzene, disulphide based compound etc.
As other light curing agent, can use for example hydroxyalkyl phenyl ketone based compound, alkyl thioxanthone based compound, sulfonium salt based compound etc.
As above-mentioned thermal curing agents; Can use organo-peroxide; Particularly, can use peroxo-diacyl system, peroxyester system, hydroperoxidation system, dialkyl system, ketone peroxide system, ketal peroxide system, alkyl super-acid ester system, peroxocarbonate based compound etc.
The usage quantity of above-mentioned solidifying agent, different because of the kind of using, usually,, preferably use with the scope of 0.1～10 mass parts with respect to aforesaid propylene acid modified amido manthanoate urea resin (1) 100 mass parts, more preferably use with the scope of 1～5 mass parts.
In addition, as above-mentioned curing catalyst, can use for example organic metal salt such as cobalt naphthenate, octylenic acid cobalt, amine system, beta-diketon class etc.
Acrylic acid modified carbamate urea resin compsn of the present invention except above-mentioned component, can contain other additive in the scope of not damaging effect of the present invention.
As above-mentioned other additive; The viewpoint of the termination of the radical polymerization that the influence of the oxygen from prevent atmosphere causes etc.; Can use for example glycol monomethyl allyl ether, diglycol monotertiary allyl ether, Ucar 35 monoallyl ether, DPG monoallyl ether, 1, the allyl ether compound of polyalcohols such as 2-butyleneglycol monoallyl ether, TriMethylolPropane(TMP) diallyl ether, glycerine diallyl ether, tetramethylolmethane three allyl ethers etc.
In addition, as above-mentioned other additive, the thermotolerance of the molding that obtains from improvement, the viewpoint of weather resistance can be used acrylic compounds.
As the aforesaid propylene acid compounds; For example can use with as the identical compound, 1 of the illustrative compound of aforesaid propylene acid compounds (D); 6-pinakon two (methyl) propenoate, 1, multifunctional acrylic compounds such as 4-butyleneglycol two (methyl) propenoate, ethylene glycol bisthioglycolate (methyl) propenoate, tripropylene glycol two (methyl) propenoate, NSC 6366 two (methyl) propenoate, Tetraglycol 99 two (methyl) propenoate, triglycol two (methyl) propenoate, polyoxyethylene glycol two (methyl) propenoate, trimethylolpropane tris (methyl) propenoate.
In addition; As above-mentioned other additive, can in the scope of not damaging effect of the present invention, use for example known in the past various additives such as packing material, pigment, dyestuff, tensio-active agent, static inhibitor, UV light absorber, stopper, tackifier, softening agent, inhibitor, flow agent, film coalescence aid, stablizer, fire retardant.
As making acrylic acid modified carbamate urea resin compsn solidified method of the present invention, because of the kind of above-mentioned solidifying agent different.For example use the acrylic acid modified carbamate urea resin compsn of above-mentioned ultraviolet curing agent, can use general ultraviolet illumination injection device such as metal halide lamp, mercuryvapour lamp, ultraviolet LED lamp to shine the ultraviolet ray of regulation and make its curing.On the other hand, used the acrylic acid modified carbamate urea resin compsn of above-mentioned thermal curing agents, for example can use High Temperature Furnaces Heating Apparatus etc., preferably heating and make its curing under 50～250 ℃ temperature.
In addition, aforesaid propylene acid modified amido manthanoate urea resin compsn as stated, is representative with the formed material that forms various molding, can in various uses such as coating agent, tackiness agent, use.Wherein, Aforesaid propylene acid modified amido manthanoate urea resin compsn; Because therefore thermotolerance, solvent resistance excellence suit in the manufacturing of the molding such as member that require the various mechanicalss of formation such as building slabs such as the telltale of designability, bath, automobile component, medical member, electronic motor member, to use.
As the method for aforesaid propylene acid modified amido manthanoate urea resin composition molding being made molding, but application examples like compression molding method, injection moulding, RTM (resin transfer moulding) method of forming, the continuously shaped method of having used heating mould, draw the method for forming etc.
Make the method for film or flaky molding as using aforesaid propylene acid modified amido manthanoate urea resin compsn; Preference as for example adopt at the demoulding substrate surface curtain formula flow slit coater methods such as coating machine method, mold pressing coating machine method, knife coater method, roll coater method, die slot coating machine method, particularly through the sour modified amido manthanoate of coating aforesaid propylene urea resin compsns such as mold pressing coating machine methods; As required after the drying, irradiation ultraviolet radiation etc. or heating and solidified method.
The molding that obtains by above method; Because solvent resistance and excellent heat resistance, therefore can be, in various uses such as the epidermal area of packing purposes, leather-like sheet, film that the middle layer forms usefulness or sheet material, use at molding such as telltale, bath for example, building slab, trolley part, household electrical appliances parts, medical apparatus parts, various container.
In addition; Aforesaid propylene acid modified amido manthanoate urea resin compsn is used under the situation of coating agent, tackiness agent; As the method that they is applied to various substrate surfaces, can enumerate for example slit coater method, knife coater method, roll coater methods etc. such as the mobile coating machine method of curtain formula, mold pressing coating machine method.
After adopting the aforesaid method coating,,, as stated,,, can form tunicle, bonding coat through heating or irradiation ultraviolet radiation etc. according to the kind of the solidifying agent that uses as the method that is cured as required with solvent seasoning.Need to prove the seasoning at normal temperatures of above-mentioned drying, but also heat drying.Heat drying is preferred to carry out in the time about with 1～600 second under 40～250 ℃ usually.
The tunicle, the bonding coat that adopt aforesaid method to form because above-mentioned solvent resistance and excellent heat resistance, therefore also can be used for the surface-coated, bonding of various base materials such as metal base, plastic basis material, wood substrate for example.
Embodiment
[embodiment 1]
In possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger; Polycarbonate polyol (UC-100, the OH value of the emerging product of space portion (strain) system: 116.4) 500.0 mass parts of packing into and containing aliphatics ring type structure; Add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1447.2 mass parts; After the toluene of dinethylformamide and 543.1 mass parts mixes; Mix with the isophorone diamine of 73.6 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; With above-mentioned carbamate urea prepolymers solution and vinylformic acid 2-hydroxy methacrylate 8.1 mass parts and the mixing of sec-butyl alcohol 241.2 mass parts; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the I) (equivalent weight of acryl: 1.15 * 10 4, weight-average molecular weight: 21000, non-volatile content: 25 quality %).
[embodiment 2]
Polycarbonate polyol (UC-100, the OH value of the emerging product of space portion (strain) system: 116.4) 500.0 mass parts of in possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger, packing into and containing aliphatics ring type structure; Add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1445.9 mass parts; After the toluene of dinethylformamide, 542.4 mass parts mixes; Mix with 75.2 mass parts of isophorone diamine, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 5.8 mass parts and sec-butyl alcohol 241.0 mass parts are mixed; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the II) (equivalent weight of acryl: 1.61 * 10 4, weight-average molecular weight: 39000, non-volatile content: 25 quality %).
[embodiment 3]
In possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger; Polycarbonate polyol (UC-100, the OH value of the emerging product of space portion (strain) system: 116.4) 500.0 mass parts of packing into and containing aliphatics ring type structure; Add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1444.6 mass parts; After the toluene of dinethylformamide and 541.7 mass parts mixes; Mix with the isophorone diamine of 76.8 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 3.5 mass parts and sec-butyl alcohol 240.8 mass parts are mixed; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the III) (equivalent weight of acryl: 2.66 * 10 4, weight-average molecular weight: 64000, non-volatile content: 25 quality %).
[embodiment 4]
Polycarbonate polyol (UC-100, the OH value of the emerging product of space portion (strain) system: 116.4) 500.0 mass parts of in possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger, packing into and containing aliphatics ring type structure; Add 4; 4 '-dicyclohexyl methane diisocyanate, 262.4 mass parts, toluene 190.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1516.8 mass parts; After the toluene of dinethylformamide, 567.8 mass parts mixes; Mix with the isophorone diamine of 76.8 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 3.5 mass parts and sec-butyl alcohol 252.8 mass parts are mixed; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the IV) (equivalent weight of acryl: 2.80 * 10 4, weight-average molecular weight: 128000, non-volatile content: 25 quality %).
[embodiment 5]
Polycarbonate polyol (UC-100, the OH value of the emerging product of space portion (strain) system: 116.4) 500.0 mass parts of in possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger, packing into and containing aliphatics ring type structure; Add 4; 4 '-dicyclohexyl methane diisocyanate, 262.4 mass parts, toluene 190.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1549.3 mass parts; After the toluene of dinethylformamide, 584.1 mass parts mixed, with 4 of 94.9 mass parts, 4 '-dicyclohexyl methyl hydride diamines mixed; Reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 3.5 mass parts and sec-butyl alcohol 258.2 mass parts are mixed; Reacted about 1 hour down at 70 ℃, obtained acrylic acid modified carbamate urea resin compsn (the V) (equivalent weight of acryl: 2.86 * 10 4, weight-average molecular weight: 172000, non-volatile content: 25 quality %).
[embodiment 6]
In possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger; Pack into and make 1; The reaction of 4-cyclohexanedimethanol and hexanodioic acid and the polyester polyol that the contains aliphatics ring type structure (OH value: 112.2) 500.0 mass parts that obtains; Add 4; 4 '-dicyclohexyl methane diisocyanate, 262.4 mass parts, toluene 190.6 mass parts, limit suppress the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1516.8 mass parts; After the toluene of dinethylformamide, 567.8 mass parts mixes; Mix with the isophorone diamine of 76.8 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 3.5 mass parts and sec-butyl alcohol 252.8 mass parts are mixed; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the VI) (equivalent weight of acryl: 2.80 * 10 4, weight-average molecular weight: 157000, non-volatile content: 25 quality %).
[comparative example 1]
Polycarbonate polyol (UC-100, the OH value of the emerging product of space portion (strain) system: 116.4) 500.0 mass parts of in possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger, packing into and containing aliphatics ring type structure; Add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1442.6 mass parts; After the toluene of dinethylformamide, 540.7 mass parts mixes; Mix with the isophorone diamine of 79.2 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; The sec-butyl alcohol of above-mentioned carbamate urea prepolymers solution and 240.4 mass parts is mixed; Reacted about 1 hour down at 70 ℃; Thereby obtained carbamate urea resin compsn (VII) (equivalent weight of acryl :-, weight-average molecular weight: 70000, non-volatile content: 25 quality %).
[comparative example 2]
In possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger, pack 1 into; The 6-pinakon is polycarbonate polyol (" ニ Star Port ラ Application 981 ", the OH value of Japanese polyurethane industry (strain) system: 112.2) 500.0 mass parts; Add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1444.6 mass parts; After the toluene of dinethylformamide, 541.7 mass parts mixes; Mix with the isophorone diamine of 76.8 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 3.5 mass parts and sec-butyl alcohol 240.8 mass parts are mixed; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the VIII) (equivalent weight of acryl: 2.66 * 10 4, weight-average molecular weight: 61000, non-volatile content: 25 quality %).
[comparative example 3]
Polycarbonate polyol (UC-100, the OH value of the emerging product of space portion (strain) system: 116.4) 500.0 mass parts of in possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger, packing into and containing aliphatics ring type structure; Add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1355.1 mass parts; After the toluene of dinethylformamide, 497.0 mass parts mixes; Mix with the quadrol of 27.1 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 3.5 mass parts and sec-butyl alcohol 225.8 mass parts are mixed; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the IX) (equivalent weight of acryl: 2.50 * 10 4, weight-average molecular weight: 59000, non-volatile content: 25 quality %).
[comparative example 4]
In possessing 5 liters four-hole boiling flask of TM, stirrer, rare gas element introducing port and reflux exchanger, pack into and make 1; The reaction of 4-butyleneglycol and hexanodioic acid and the polyester polyol (OH value: 112.2) 500.0 mass parts that obtains; Add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts; The limit suppresses the heat release limit reacted 3 hours down at 80 ℃, thereby had obtained having in molecular end the toluene solution of the carbamate prepolymer of NCO.
Next; With being cooled to 40 ℃ above-mentioned toluene solution, the N of 1444.6 mass parts; After the toluene of dinethylformamide and 541.7 mass parts mixes; Mix with the isophorone diamine of 76.8 mass parts, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of NCO.
Next; Above-mentioned carbamate urea prepolymers solution, vinylformic acid 2-hydroxy methacrylate 3.5 mass parts and sec-butyl alcohol 240.8 mass parts are mixed; Reacted about 1 hour down at 70 ℃, thereby obtained acrylic acid modified carbamate urea resin compsn (the X) (equivalent weight of acryl: 2.66 * 10 4, weight-average molecular weight: 64000, non-volatile content: 25 quality %).
[measuring method of the weight-average molecular weight of acrylic acid modified carbamate urea resin]
The weight-average molecular weight of the acrylic acid modified carbamate urea resin that obtains in last note embodiment and the comparative example converts through the polystyrene standard that adopts gel permeation chromatography (GPC) and obtains.The solids component 0.4g of the acrylic acid modified carbamate urea resin compsn that obtains is dissolved in THF 100g and processes the mensuration sample.
Determinator has used eastern groove (strain) system performance liquid chromatography HLC-8220 type.Chromatographic column is used eastern Cao (strain) system post TSK-GEL (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL) combination.
As condition determination, column temperature is 40 ℃, and elutriant is a THF, and flow is 1.0mL/ minute, and sample size is 500 μ L, and polystyrene standard has used the TSK polystyrene standard.
[making method of molding (film)]
With respect to solids component 100 mass parts of the resin combination that obtains in the foregoing description and the comparative example, mix Irgacure184 (vapour crust Japan (strain) system, Photoepolymerizationinitiater initiater) 2 mass parts, stirred 10 minutes, thereby obtained coating fluid.
Above-mentioned coating fluid is being implemented on the polyethylene terephthalate film that the demoulding handles after the coating; Use hot air dryer after under 100 ℃ dry 20 minutes; Use the UV irradiation equipment (CSOT-40 of the GS Yuasa of Co., Ltd. system) of carrying type, irradiation 1000mJ/cm 2Thereby the thickness after having obtained solidifying is the film of 50 μ m.
[evaluation method of solvent resistance]
The film that adopts aforesaid method to make is cut into the size of vertical 50mm * horizontal 50mm, thereby has obtained experimental film.Next, with above-mentioned experimental film be fixed in inside dimension for the framework of vertical 40mm * horizontal 40mm not produce tension force, with it as test film.
Next, above-mentioned test film was flooded 1 minute in THF (THF) under the environment of 23 ℃ of temperature and relative humidity 50%.
Behind the above-mentioned dipping, above-mentioned test film is taken out from above-mentioned THF, estimate through visual shape to above-mentioned experimental film etc.
◎: experimental film keeps the shape before the dipping, does not also produce pinprick, albefaction on its surface.
Zero: experimental film keeps the shape before the dipping, but confirms to have pinprick, albefaction on its surface.
△: the part of experimental film (less than membrane area about 30%) dissolving.
*: the dissolving more than 50% of the total area of experimental film almost keeps the preceding film shape of dipping.
[stable on heating evaluation method]
Use Tianjin, island Flow Tester CFT500D-1 (Shimadzu Scisakusho Ltd's system); Measure to adopt the flow starting temperature of the film that aforesaid method makes, condition determination is following: measure the beginning temperature: 40 ℃, heat-up rate: 3.0 ℃/minute, temperature-raising method, cylinder pressure: 9.807 * 10 5Pa, mouthful mould: 1mm * 1mmL, load: 98N, hold-time: 600 seconds.
Above-mentioned flow starting temperature is approximately more than 180 ℃ is evaluated as excellent heat resistance.
[table 1]
Table 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Polyvalent alcohol (A) ?CH-PC CH-PC ?CH-PC ?CH-PC CH-PC
POLYMETHYLENE POLYPHENYLISOCYANATE (B) ?IPDI IPDI ?IPDI ?H12MDI H12MDI
Polyamines (C) ?IPDA IPDA ?IPDA ?IPDA H12MDA
Acrylic compounds (D) ?HEA HEA ?HEA ?HEA HEA
Solvent resistance ?○ ○ ?○ ?◎ ◎
Thermotolerance (℃) ?185 190 ?196 ?218 220
[table 2]
Table 2 Embodiment 6 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Polyvalent alcohol CH-AA ?CH-PC ?HG-PC ?CH-PC ?BG-AA
POLYMETHYLENE POLYPHENYLISOCYANATE H12MDI ?IPDI ?IPDI ?IPDI ?IPDI
Polyamines IPDA ?IPDA ?IPDA ?EDA ?IPDA
Acrylic compounds HEA ?- ?HEA ?HEA ?HEA
Solvent resistance ◎ ?× ?× ?× ?×
Thermotolerance (℃) 185 ?178 ?184 ?190 ?177
Abbreviation in the his-and-hers watches 1～2 describes.
(1,4 cyclohexane dimethanol is polycarbonate polyol, OH value to the UC-100 that " CH-PC " makes for the emerging product of space portion (strain): 116.4).
" HG-PC " is that (1, the 6-pinakon is polycarbonate polyol, OH value: 112.2) for " the ニ Star Port ラ Application 981 " of Japanese polyurethane industry (strain) system.
" BG-AA " is for making 1, the polyester polyol (OH value: 112.2) that 4-butyleneglycol and hexanodioic acid reaction obtain.
" CH-AA " the polyester polyol that contains aliphatics ring type structure (OH value: 112.2) for the reaction of 1,4 cyclohexane dimethanol and hexanodioic acid is obtained.
" IPDI " is isophorone diisocyanate.
" H12MDI " is 4,4 '-dicyclohexyl methane diisocyanate.
" IPDA " is isophorone diamine.
" EDA " is quadrol.
" H12MDA " is 4,4 '-dicyclohexyl methyl hydride diamines.
" HEA " is vinylformic acid 2-hydroxy methacrylate.
Utilize possibility on the industry
If acrylic acid modified carbamate urea resin compsn of the present invention; Can form and have excellent solvent resistance and stable on heating molding, therefore can be used in the manufacturing of the skin material etc. of for example trolley part, household electrical appliances parts, wrapping material, film, sheet material, leather-like sheet.
In addition, acrylic acid modified carbamate urea resin compsn of the present invention can form and has excellent solvent resistance and stable on heating tunicle etc., therefore can be used in the surface coated agent, tackiness agent of various base materials for example etc.

Claims (11)

1. acrylic acid modified carbamate urea resin compsn; It is characterized in that; Contain acrylic acid modified carbamate urea resin (1) and solvent (2) forms, this acrylic acid modified carbamate urea resin (1) obtains through acrylic compounds (D) reaction that makes the polyvalent alcohol (A) that contains aliphatics ring type structure, the POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure, the polyamines (C) that contains aliphatics ring type structure and have the group that contains active hydrogen atom.
2. acrylic acid modified carbamate urea resin compsn as claimed in claim 1; Wherein, mass ratio in the said acrylic acid modified carbamate urea resin compsn, said acrylic acid modified carbamate urea resin (1) and said solvent (2) is (1)/(2)=10～50/90～50.
3. according to claim 1 or claim 2 acrylic acid modified carbamate urea resin compsn; Wherein, the equivalent weight from the acryl of said acrylic compounds (D) that had of said acrylic acid modified carbamate urea resin is 10000～50000 scope.
4. like each the described acrylic acid modified carbamate urea resin compsn in the claim 1～3; Wherein, With respect to the polyvalent alcohol (A) that contains aliphatics ring type structure as the manufacturing raw material of said acrylic acid modified carbamate urea resin said, contain aliphatics ring type structure POLYMETHYLENE POLYPHENYLISOCYANATE (B), contain the polyamines (C) of aliphatics ring type structure and have the total quality of the acrylic compounds (D) of the group that contains active hydrogen atom, the mass ratio of aliphatics ring type structure is 20～60 quality %.
5. like each the described acrylic acid modified carbamate urea resin compsn in the claim 1～4, wherein, said polyvalent alcohol (A) has the OH value of 30～230mgKOH/g.
6. like each the described acrylic acid modified carbamate urea resin compsn in the claim 1～5; Wherein, the said polyvalent alcohol (A) that contains aliphatics ring type structure for be selected from polycarbonate polyol that contains aliphatics ring type structure and the polyester polyol that contains aliphatics ring type structure more than a kind.
7. acrylic acid modified carbamate urea resin compsn as claimed in claim 6, wherein, the said polycarbonate polyol that contains aliphatics ring type structure obtains through making 1,4 cyclohexane dimethanol and carbonic ether and/or phosgene reaction.
8. like each the described acrylic acid modified carbamate urea resin compsn in the claim 1～7; Wherein, The said POLYMETHYLENE POLYPHENYLISOCYANATE (B) that contains aliphatics ring type structure is to be selected from 4, in 4 '-dicyclohexyl methane diisocyanate and the isophorone diisocyanate more than a kind.
9. like each the described acrylic acid modified carbamate urea resin compsn in the claim 1～8, wherein, said (methyl) acrylic compounds (D) is for containing the alkyl acrylate of hydroxyl.
10. like each the described acrylic acid modified carbamate urea resin compsn in the claim 1～9, wherein, said acrylic acid modified carbamate urea resin (1) has 5000～200000 weight-average molecular weight.
11. a molding, it obtains each the described acrylic acid modified carbamate urea resin composition molding in the claim 1～10.
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