CN102574979B - 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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CN102574979B
CN102574979B CN201080040151.XA CN201080040151A CN102574979B CN 102574979 B CN102574979 B CN 102574979B CN 201080040151 A CN201080040151 A CN 201080040151A CN 102574979 B CN102574979 B CN 102574979B
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urea resin
type structure
ring type
modified urethane
acrylic modified
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CN102574979A (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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

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 modified urethane urea resin composition and the molding that uses it to obtain
Technical field
The present invention relates to the acrylic modified urethane urea resin composition that can use in take formed material for example, coating agent, tackiness agent as the various uses of representative.
Background technology
Use the molding that the polyurethane series formed material obtains to use in the various uses such as skin material that consist of 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.For example in the situation that use in exterior material in automobile, 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, food etc., variable color etc. acid, in addition, in the situation that long-time exposure the under the hot environment in summer, sometimes require not cause the thermotolerance of degree of the distortion etc. of molding.
as the formed material that is difficult to cause the above-mentioned distortion that results from alcohol etc. etc., the known specific prepolymer that for example obtains by making the reaction of poly-carbonic acid tetramethylene esterdiol and one kind or two or more organic diisocyanate and the chain extension agent with 2 energy and active hydrogen of the isocyanate reaction of this prepolymer form, mol ratio by above-mentioned prepolymer/chain extension agent is to surpass 1 value, carried out with the reaction terminating material of the active hydrogen of the unreacting isocyanate reaction with 1 energy and end of above-mentioned prepolymer that end stops, molecular weight 3～200,000 and gel % are thermoplastic polyurethane formed material (reference example such as the patent documentation 1 below 5%.)。
But, the molding that uses above-mentioned thermoplastic polyurethane formed material to obtain, aspect thermotolerance, sometimes not enough in practical, long-term exposure causes distortion etc. sometimes in the situation under 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 for having bonding between the member that the molding of the shape of regulation consists of.
But contained organic solvent in above-mentioned tackiness agent is invaded the surface of polyurethane series molding sometimes, causes the dissolving, distortion, variable color on this molding surface etc.
With the above-mentioned molding of membranaceous or sheet with an organic solvent in stacked etc. the situation of type tackiness agent, due to Effects of organic solvents contained in above-mentioned tackiness agent, sometimes cause distortion and the variable colors such as dissolving, contraction of film etc. when special.
Like this, industrial community requires a kind of formed material that can form following molding of exploitation, even this molding possesses solvent resistance and the above-mentioned thermotolerance of the degree of the dissolving that also do not cause in these cases the molding surface, distortion, variable color etc.
But, the molding that uses in above-mentioned patent documentation 1 the above-mentioned thermoplastic polyurethane formed material of record to obtain, although have good patience for lubricant components such as alcohol, oleic acid, but for the various organic solvents take strong solvent as representative, possess hardly enough solvent resistances, be difficult to still sometimes to prevent that the resin that causes adhering to of above-mentioned solvent is from the distortion on the dissolving on molding surface, molding surface, variable color etc.
As previously discussed, although 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 yet to find in the urgent need to a kind of can formation.
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 solvent resistance and the thermotolerance of excellence of the degree of the dissolving that also do not cause the molding surface in the situation that all kinds of SOLVENTS adheres to, distortion, variable color etc. concurrently.
Be used for solving 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, polyisocyanates, but also studied the combination with various chain extension agents.
It found that, so long as contain in the situation of acrylic modified urethane urea resin composition of the acrylic modified urethane urea resin that makes the polyvalent alcohol, the polyisocyanates 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.
namely, the molding that the present invention relates to acrylic modified urethane urea resin composition and used said composition to form, described composition is characterised in that, contain acrylic modified urethane urea resin (1) and solvent (2), this acrylic modified urethane urea resin (1) is by making the polyvalent alcohol (A) that contains aliphatics ring type structure, the polyisocyanates (B) that contains aliphatics ring type structure, contain the polyamines (C) of aliphatics ring type structure and have acrylic compounds (D) reaction of the group that contains active hydrogen atom and obtain.
The effect of invention
So long as acrylic modified urethane urea resin composition of the present invention, just can form and possess excellent solvent resistance and stable on heating molding, therefore can use in the manufacturing such as the skin material of trolley part, household electrical appliances parts, wrapping material, film, sheet material, leather-like sheet etc.
In addition, acrylic modified urethane urea resin composition of the present invention possesses excellent solvent resistance and stable on heating tunicle etc. owing to forming, therefore can use in such as the surface coated agent of various base materials, tackiness agent etc.
Embodiment
At first, the acrylic modified urethane urea resin (1) that uses in the present invention is described.
The acrylic modified urethane urea resin that uses in the present invention (1) obtains by acrylic compounds (D) reaction that makes the polyvalent alcohol (A) that contains aliphatics ring type structure and the polyisocyanates (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 is all important by the above-mentioned polyvalent alcohol that contains aliphatics ring type structure and each the supply that contains the polyisocyanates of aliphatics ring type structure and contain the polyamines of aliphatics ring type structure.For example, even the mass ratio of the aliphatics ring type structure that exists in aforesaid propylene acid modified amido manthanoate urea resin (1) is equal extent, but replace containing the polyisocyanates of aliphatics ring type structure and used in the resin combination of aliphatic polyisocyante, sometimes can not form the molding that possesses required solvent resistance.
As aforesaid propylene acid modified amido manthanoate urea resin (1), from obtaining having concurrently excellent solvent resistance and the viewpoint of stable on heating molding, the preferred material that uses the aliphatics ring type structure of the scope with 20～60 quality %.Need to prove, the mass ratio of above-mentioned aliphatics ring type structure, refer to 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 polyisocyanates (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 in the situation of the so-called urethane acrylate that does not have the urea key, forming process is low sometimes, is difficult to the molding such as film of Production Example such as thin-walled property.Therefore, as aforesaid propylene acid modified amido manthanoate urea resin (1), forming process from excellence, the viewpoint that has simultaneously good thermotolerance and solvent resistance concurrently is set out, the preferred acrylic modified urethane urea resin that uses the urea key with 4～10 quality %, this ratio is 5～8 quality % more preferably, are particularly preferably 6～7 quality %.Need to prove, the mass ratio of above-mentioned urea key, refer to contain the polyvalent alcohol (A) of aliphatics ring type structure and contain the polyisocyanates (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 with respect to the raw material that uses in the manufacturing as aforesaid propylene acid modified amido manthanoate urea resin (1) above-mentioned 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 from excellence, the viewpoint that has simultaneously good thermotolerance and solvent resistance concurrently is set out, the preferred acrylic modified urethane urea resin that uses the amino-formate bond with 5～15 quality %, this ratio is 7～9 quality % more preferably.Need to prove, the mass ratio of above-mentioned amino-formate bond, refer to contain the polyvalent alcohol (A) of aliphatics ring type structure and contain the polyisocyanates (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 with respect to the raw material that uses in the manufacturing as aforesaid propylene acid modified amido manthanoate urea resin (1) above-mentioned the quality of carbamate bond structure shared ratio in above-mentioned raw materials.
As aforesaid propylene acid modified amido manthanoate urea resin (1), in solvent resistance and the stable on heating while of excellence, keep good forming process aspect, the preferred acrylic modified urethane urea resin with weight-average molecular weight of 5000～200000, more preferably 15000～200000 the scope used.Need to prove, the weight-average molecular weight of aforesaid propylene acid modified amido manthanoate urea resin (1) is to use gel permeation chromatography (GPC), uses tetrahydrofuran (THF) as elutriant, the value that adopts vinylbenzene to convert and obtain.
The acrylic modified urethane urea resin that uses in the present invention (1); 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 modified urethane 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, refer to the polyvalent alcohol that contains aliphatics ring type structure (A) that consists of aforesaid propylene acid modified amido manthanoate urea resin (1) and contain the polyisocyanates (B) of aliphatics ring type structure and the total quality of acrylic compounds (D) that contains 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 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 in the present invention, preferably using hydroxyl value is the material of the scope of 30～230mgKOH/g, more preferably uses the material of the scope that is 50～230mgKOH/g.Need to prove, the hydroxyl 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 such as the polycarbonate polyol that contains aliphatics ring type structure, contain aliphatics ring type structure polyester polyol, contain aliphatics ring type structure polyether glycol, 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 the polycarbonate polyol that contains aliphatics ring type structure and the polyester polyol that contains aliphatics ring type structure, particularly preferably use the polycarbonate diol that contains aliphatics ring type structure and the polyester glycol that contains aliphatics ring type structure.
As the above-mentioned polycarbonate polyol that contains aliphatics ring type structure, can use the polyvalent alcohol that contains aliphatics ring type structure (a1) reaction of the lower molecular weight that for example makes carbonic ether and/or phosgene and about 50～400 left and right described later and the product that obtains.
As above-mentioned carbonic ether, can use such as methyl carbonate, methylcarbonate, ethyl-carbonate, diethyl carbonate, cyclic carbonate ester, diphenyl carbonate etc.
as can with above-mentioned carbonic ether, the polyvalent alcohol that contains aliphatics ring type structure (a1) of phosgene reaction, for example can use 1, the 2-cyclobutanediol, 1, 3-encircles pentanediol, 1, the 4-cyclohexanediol, the ring heptanediol, the ring ethohexadiol, 1, the 4-cyclohexanedimethanol, the 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] dodecane-di-alcohol, hydroxypropyl three rings [5, 3, 1, 1] dodecanol, spiral shell [3, 4] ethohexadiol, the butyl cyclohexanediol, 1, 1 '-bicyclohexylidene base glycol, phloroglucitol, Hydrogenated Bisphenol A, 1, 3-diamantane glycol etc., wherein preferably use 1, the 4-cyclohexanedimethanol.
As the above-mentioned polyester polyol that contains aliphatics ring type structure, can use the product that obtains such as the polyvalent alcohol that contains aliphatics ring type structure of the lower molecular weight that makes about 50～400 left and right and polycarboxylic acid reaction or make low molecular polylol and contain the polycarboxylic acid reaction of aliphatics ring type structure and the cyclic ester compounds such as the part of the product that obtains or above-mentioned product and 6-caprolactone, γ-valerolactone carry out ring-opening polymerization and the product of addition etc.
As the polyvalent alcohol that contains aliphatics ring type structure that can use in the manufacturing of the above-mentioned polyester polyol that contains aliphatics ring type structure, can use with as the same polyvalent alcohol that contains aliphatics ring type structure of the illustrative polyvalent alcohol (a1) that contains aliphatics ring type structure of the polyvalent alcohol that contains aliphatics ring type structure that uses in the manufacturing of the above-mentioned polycarbonate polyol that contains aliphatics ring type structure.
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 for example succsinic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, the aliphatics polycarboxylic acid of dimeracid, 1, the 4-cyclohexane cyclohexanedimethanodibasic, hexanaphthene tricarboxylic acid etc. contains the polycarboxylic acid of aliphatics ring type structure, phthalic acid, m-phthalic acid, terephthalic acid, 1, the 4-naphthalic acid, 2, the 3-naphthalic acid, 2, the 6-naphthalic acid, biphenyl dicarboxylic acid, trimellitic acid, the aromatic polycarboxylic acids such as pyromellitic acid, and these acid anhydrides or ester derivative are separately or more than 2 kinds and use, the preferred aliphatics polycarboxylic acid that uses.
The polycarboxylic acid that contains aliphatics ring type structure as using in the manufacturing of the above-mentioned polyester polyol that contains aliphatics ring type structure with similarly 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 ethylene glycol, glycol ether, triglycol, Tetraglycol 99, 1,2-PD, 1,3-PD, dipropylene glycol, tripropylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,5-PD, 1,5-hexylene glycol, 1,6-hexylene glycol, 2,5-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane glycol, 1,12-dodecanediol, the 2-methyl isophthalic acid, ammediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-PD, the 3-methyl isophthalic acid, the 5-pentanediol, 2-ethyl-1, the 3-hexylene glycol, the 2-methyl isophthalic acid, the 8-ethohexadiol, glycerine, TriMethylolPropane(TMP), one contracting two (TriMethylolPropane(TMP)s), two contracting three (TriMethylolPropane(TMP)s), the aliphatic polyols such as tetramethylolmethane etc.
As the above-mentioned polyether glycol that contains aliphatics ring type structure, for example can use with the one kind or two or more compound with 2 above active hydrogen atoms as initiator the polyether glycol that the oxyalkylene addition polymerization is obtained.
As above-mentioned initiator, can use the initiator same with the above-mentioned polyvalent alcohol that contains aliphatics ring type structure (a1) such as Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F, 1,4 cyclohexane dimethanol etc. and so on.In addition, as required, also can be with present known ethylene glycol, glycol ether, triglycol, propylene glycol, trimethylene, 1,3 butylene glycol, 1,4-butyleneglycol, 1, the aliphatic polyols such as 6-hexylene glycol, neopentyl glycol, glycerine, trimethylolethane, TriMethylolPropane(TMP) are also used.
As above-mentioned oxyalkylene, can use such as ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min., Epicholorohydrin, tetrahydrofuran (THF) etc.
As the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure, due to the molding that can form solvent resistance, thermotolerance, excellent in te pins of durability, therefore preferred the and above-mentioned polycarbonate polyol that contains aliphatics ring type structure, contain the polyester polyol of aliphatics ring type structure or contain the chain extension agent that contains active hydrogen that is used in combination other together with the polyether glycol etc. of aliphatics ring type structure.
As above-mentioned other the chain extension agent that contains active hydrogen, can be with for example ethylene glycol, 1,2-propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 3,3 '-dihydroxymethyl heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3, the polyvalent alcohols such as two (hydroxymethyl) heptane of 3-, glycol ether, dipropylene glycol, glycerine, TriMethylolPropane(TMP), sorbyl alcohol, quinhydrones two (hydroxyethyl) ether etc. are used singly or two or more kinds in combination.
In the present invention, except the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure, other polyvalent alcohols 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 can be used in combination 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 modified urethane urea resin of the present invention (1) with contain the polyisocyanates (B) of aliphatics ring type structure and contain the polyamines (C) of aliphatics ring type structure and the total quality of acrylic compounds (D), use in the scope of 40～80 quality %.
Below, the above-mentioned polyisocyanates (B) that contains aliphatics ring type structure is described.
As the above-mentioned polyisocyanates (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 solvent resistance and the stable on heating viewpoint of giving molding excellence of the present invention, preferably use vulcabond, more preferably use isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate particularly preferably uses HMDI.
In addition, in the present invention, except the above-mentioned polyisocyanates (B) that contains aliphatics ring type structure, other the polyisocyanates such as aliphatic polyisocyantes such as the aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate can be used in combination as required.
The above-mentioned polyisocyanates (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 modified urethane urea resin (1) that obtains with contain the polyisocyanates (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 use in the scope of 15～50 quality %.
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, diamino-cyclohexane, methyl diamino-cyclohexane, piperazine, norbornylene diamines etc., wherein from the viewpoint of the molding that forms excellent heat resistance and solvent resistance excellence, the preferred diamines that uses, particularly preferably use isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines.
In addition, in the present invention, except the above-mentioned polyamines (C) that contains aliphatics ring type structure, as required, can be with in the past quadrol etc. in the scope of not damaging effect of the present invention 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 modified urethane urea resin (1) that obtains with contain the polyisocyanates (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 use in the scope of 1～20 quality %.
Next, above-mentioned acrylic compounds (D) with the group that contains active hydrogen atom is described.
The acrylic compounds with the group that contains active hydrogen atom (D) of using in the present invention; 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 such as hydroxyl, carboxyl etc., be preferably hydroxyl.
As aforesaid propylene acid compounds (D), can use the acrylic compounds with above-mentioned hydroxyl, the acrylic compounds with carboxyl etc., the preferred use has the acrylic compounds of hydroxyl.
As the acrylic compounds with above-mentioned hydroxyl, can use such as (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 the alkyl acrylate of hydroxyl, polyethylene glycol monoacrylate, polypropylene glycol mono acrylic ester etc.Wherein, from solvent resistance and stable on heating viewpoint, the preferred alkyl acrylate that contains hydroxyl that uses, the viewpoint of the easiness 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 modified urethane urea resin (1) with contain the polyisocyanates (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 use in the scope of 0.05～10 quality %.
In addition, the part of aforesaid propylene acid compounds (D) in acrylic modified urethane urea resin composition of the present invention, can exist with unreacted state.That is, acrylic modified urethane urea resin composition of the present invention together with aforesaid propylene acid modified amido manthanoate urea resin, can contain unreacted aforesaid propylene acid compounds (D).
Next, the solvent (2) that uses in 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), in situation with an organic solvent, be not particularly limited, can use for example vinyl acetic monomer, N-BUTYL ACETATE, ethyl lactate, cellosolve, cellosolve acetate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, toluene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, acetonitrile, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, the N-ethyl pyrrolidone, methyl alcohol, Virahol, the 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 acrylic modified urethane urea resin composition 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 manufacture method of aforesaid propylene acid modified amido manthanoate urea resin (1) described.
As the manufacture method of aforesaid propylene acid modified amido manthanoate urea resin (1), can enumerate the method for for example following method for making (i)～method for making (ii).Wherein, owing to easily controlling reaction, the preferred method manufacturing of adopting following (i).
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 polyisocyanates (B) of aliphatics ring type structure and as required above-mentioned other the chain extension agent reaction that contains active hydrogen and obtain having in molecular end the carbamate prepolymer of isocyanate group, next, make acrylic modified urethane urea resin (1) by making above-mentioned carbamate prepolymer and above-mentioned polyamines (C) and aforesaid propylene acid compounds (D) reaction that contains aliphatics ring type structure.
Above-mentioned polyvalent alcohol (A) and the above-mentioned reaction that contains the polyisocyanates (B) of aliphatics ring type structure that contains aliphatics ring type structure, preferably at hydroxyl that this polyvalent alcohol (A) that contains aliphatics ring type structure has and the equivalent ratio [isocyanate group/hydroxyl] that contains the isocyanate group that the polyisocyanates (B) of aliphatics ring type structure has carry out under the scope of 1.1/1.0～5.0/1.0, the scope of 1.5/1.0～3.0/1.0 more preferably.In addition, above-mentioned polyvalent alcohol (A) and the above-mentioned reaction that contains the polyisocyanates (B) of aliphatics ring type structure that contains aliphatics ring type structure preferably carried out under the condition of 20～120 ℃ about about 30 minutes～24 hours.
contain the polyvalent alcohol (A) of aliphatics ring type structure and contain that the reaction of the polyisocyanates (B) of aliphatics ring type structure obtains by above-mentioned, the carbamate prepolymer and the above-mentioned reaction that contains polyamines (C) and the aforesaid propylene acid compounds (D) of aliphatics ring type structure that have isocyanate group in above-mentioned molecular end, for example, can be by disposable or successively supply with above-mentioned carbamate prepolymer and above-mentionedly contain the polyamines (C) of aliphatics ring type structure and make its reaction, thereby make the carbamate urea prepolymers, again by making the reaction of this carbamate urea prepolymers and aforesaid propylene acid compounds (D), thereby make acrylic modified urethane urea resin (1).At this moment, the isocyanate group that has of above-mentioned carbamate prepolymer and the equivalent ratio [amino/isocyanate group] of amino that contains the polyamines (C) of aliphatics ring type structure are preferably the scope of 0.70/1.0～0.99/1.0.In addition, also can by 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 successively mix, make in about about 1～3 hour of reaction under the condition of 20～80 ℃.
in addition, above-mentioned method for making (ii) is following method: under above-mentioned solvent (2), make above-mentioned polyisocyanates (B) and above-mentioned polyamines (C) reaction that contains aliphatics ring type structure that contains aliphatics ring type structure, thereby obtain having in molecular end the polyureas prepolymer of isocyanate group, next, make this polyureas prepolymer and the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure and aforesaid propylene acid compounds (D) and above-mentioned other the chain extension agent reaction that contains active hydrogen as required, thereby make acrylic modified urethane urea resin (1).
Above-mentioned polyisocyanates (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 [isocyanate group/amino] of the amino that preferably has at isocyanate group that the above-mentioned polyisocyanates (B) that contains aliphatics ring type structure has 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 polyisocyanates (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 the condition of 20～80 ℃ about about 30 minutes～1 hour.
obtained by the above-mentioned polyisocyanates (B) that contains aliphatics ring type structure and the above-mentioned reaction that contains the polyamines (C) of aliphatics ring type structure, the polyureas prepolymer and the above-mentioned reaction that contains polyvalent alcohol (A) and the aforesaid propylene acid compounds (D) of aliphatics ring type structure that have isocyanate group in above-mentioned molecular end, for example, can be by disposable or successively supply with above-mentioned polyureas prepolymer 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 isocyanate group, by making the reaction of this carbamate urea prepolymers and aforesaid propylene acid compounds (D), thereby make acrylic modified urethane urea resin (1).In addition, also can be by above-mentioned polyureas prepolymer and the above-mentioned polyvalent alcohol (A) that contains aliphatics ring type structure and aforesaid propylene acid compounds (D) is disposable or successively mix and its reaction is made.
When making aforesaid propylene acid modified amido manthanoate urea resin (1), in above-mentioned method for making (i) and situation (ii), all can promote reaction with tertiary amine catalyst, organo-metallic series catalysts as required.
Contain the acrylic modified urethane urea resin (1) that obtained by above method and the acrylic modified urethane urea resin composition of the present invention of solvent (2), can contain as required solidifying agent, curing catalyst.
As above-mentioned solidifying agent, can use light curing agent, thermal curing agents such as ultraviolet curing agent, electrocuring agent.
Above-mentioned ultraviolet curing agent is light sensitizing material, and for example can using, the such benzoin ether of benzoin alkylether is; The benzophenone series such as benzophenone, 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, the methyl phenyl ketones such as 1-dichloroacetophenone are; The thioxanthone based compounds such as CTX, 2-methyl thioxanthone, ITX.
As above-mentioned electrocuring agent, can use such as haloalkyl benzene, disulphide based compound etc.
As other light curing agent, can use such as 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 that peroxidation diacyl system, peroxyester system, hydroperoxidation system, dialkyl system, ketone peroxide system, ketal peroxide are, 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, with respect to aforesaid propylene acid modified amido manthanoate urea resin (1) 100 mass parts, preferably use with the scope of 0.1～10 mass parts, more preferably use with the scope of 1～5 mass parts.
In addition, as above-mentioned curing catalyst, can use organic metal salts such as cobalt naphthenate, octylenic acid cobalt, amine system, beta-diketon class etc.
Acrylic modified urethane urea resin composition 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 effect of oxygen from prevent atmosphere causes etc., can use for example glycol monomethyl allyl ether, diglycol monotertiary allyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, 1, the allyl ether compound of the 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 illustrative Compound Phase of aforesaid propylene acid compounds (D) with compound, 1, 6-hexylene glycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, triglycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, the multifunctional acrylic compounds such as trimethylolpropane tris (methyl) acrylate.
In addition, as above-mentioned other additive, can use in the scope of not damaging effect of the present invention such as the known various additives in the past such as packing material, pigment, dyestuff, tensio-active agent, static inhibitor, UV light absorber, stopper, tackifier, softening agent, antioxidant, flow agent, film coalescence aid, stablizer, fire retardant.
As the method that acrylic modified urethane urea resin composition of the present invention is solidified, because of the kind of above-mentioned solidifying agent different.For example use the acrylic modified urethane urea resin composition of above-mentioned ultraviolet curing agent, can use the 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 modified urethane urea resin composition of above-mentioned thermal curing agents, can use such as High Temperature Furnaces Heating Apparatus etc., preferably heating and make its curing at the temperature of 50～250 ℃.
In addition, aforesaid propylene acid modified amido manthanoate urea resin composition as mentioned above, take the formed material that forms various molding as representative, can use in the various uses such as coating agent, tackiness agent.Wherein, aforesaid propylene acid modified amido manthanoate urea resin composition, due to thermotolerance, solvent resistance excellence, therefore use in the manufacturing of the suitable molding such as member requiring the various mechanicalss of formation such as the building slabs such as the counter of designability, bath, automobile component, medical member, electronic motor member.
As aforesaid propylene acid modified amido manthanoate urea resin composition molding being made the method for molding, but application examples as 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 the molding of film or sheet as using aforesaid propylene acid modified amido manthanoate urea resin composition; preference as adopt the slit coater methods such as coating machine method, mold pressing coating machine method that flow such as the curtain formula, knife coater method, roll coater method, die slot coating machine method at demoulding substrate surface, particularly by the sour modified amido manthanoate of coating aforesaid propylene urea resin compositions such as mold pressing coating machine methods; as required after drying, irradiation ultraviolet radiation etc. or heating and the method for solidifying.
The molding that is obtained by above method, due to solvent resistance and excellent heat resistance, therefore can use in the various uses such as molding such as counter, bath, building slab, trolley part, household electrical appliances parts, medical apparatus parts, various container, the film that forms use towards the epidermal area of packing purposes, leather-like sheet, middle layer or sheet material.
In addition, aforesaid propylene acid modified amido manthanoate urea resin composition is used in the situation of coating agent, tackiness agent, as they being applied to the method for various substrate surfaces, can enumerate flow such as the curtain formula slit coater method, knife coater method, the roll coater methods etc. such as coating machine method, mold pressing coating machine method.
After adopting the aforesaid method coating, as required with solvent seasoning, as the method that is cured, as mentioned above, according to the kind of the solidifying agent that uses, by heating or irradiation ultraviolet radiation etc., can form tunicle, bonding coat.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 due to 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.
Embodiment
[embodiment 1]
In possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger, polycarbonate polyol (UC-100, the hydroxyl value of the emerging product of space section (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, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1447.2 mass parts will be cooled to, 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 isocyanate group.
Next; with above-mentioned carbamate urea prepolymers solution and vinylformic acid 2-hydroxy methacrylate 8.1 mass parts and sec-butyl alcohol 241.2 mass parts mixing; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (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 hydroxyl value of the emerging product of space section (strain) system: 116.4) 500.0 mass parts of packing in possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger and containing aliphatics ring type structure, add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1445.9 mass parts will be cooled to, 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 isocyanate group.
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; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (the II) (equivalent weight of acryl: 1.61 * 10 4, weight-average molecular weight: 39000, non-volatile content: 25 quality %).
[embodiment 3]
In possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger, polycarbonate polyol (UC-100, the hydroxyl value of the emerging product of space section (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, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1444.6 mass parts will be cooled to, 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 isocyanate group.
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; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (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 hydroxyl value of the emerging product of space section (strain) system: 116.4) 500.0 mass parts of packing in possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger and containing aliphatics ring type structure, add 4,4 '-dicyclohexyl methane diisocyanate, 262.4 mass parts, toluene 190.6 mass parts, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1516.8 mass parts will be cooled to, 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 isocyanate group.
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; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (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 hydroxyl value of the emerging product of space section (strain) system: 116.4) 500.0 mass parts of packing in possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger and containing aliphatics ring type structure, add 4,4 '-dicyclohexyl methane diisocyanate, 262.4 mass parts, toluene 190.6 mass parts, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1549.3 mass parts will be cooled to, after the toluene of dinethylformamide, 584.1 mass parts mixes, with 4 of 94.9 mass parts, 4 '-dicyclohexyl methyl hydride diamines mixes, reaction is 3 hours under 60 ℃, thereby has obtained having in molecular end the carbamate urea prepolymers solution of isocyanate group.
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; reaction under 70 ℃ about 1 hour, obtained acrylic modified urethane urea resin composition (the V) (equivalent weight of acryl: 2.86 * 10 4, weight-average molecular weight: 172000, non-volatile content: 25 quality %).
[embodiment 6]
In possessing the four-hole boiling flask of 5 liters of thermometer, 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 (hydroxyl value: 112.2) 500.0 mass parts that obtains, add 4,4 '-dicyclohexyl methane diisocyanate, 262.4 mass parts, toluene 190.6 mass parts, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1516.8 mass parts will be cooled to, 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 isocyanate group.
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; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (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 hydroxyl value of the emerging product of space section (strain) system: 116.4) 500.0 mass parts of packing in possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger and containing aliphatics ring type structure, add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1442.6 mass parts will be cooled to, 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 isocyanate group.
Next; the sec-butyl alcohol of above-mentioned carbamate urea prepolymers solution and 240.4 mass parts is mixed; reaction under 70 ℃ about 1 hour; thereby obtained carbamate urea resin composition (VII) (equivalent weight of acryl :-; weight-average molecular weight: 70000, non-volatile content: 25 quality %).
[comparative example 2]
Pack 1 in possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger, the 6-hexylene glycol is polycarbonate polyol (" ニ Star Port ラ Application 981 ", the hydroxyl 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, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1444.6 mass parts will be cooled to, 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 isocyanate group.
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; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (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 hydroxyl value of the emerging product of space section (strain) system: 116.4) 500.0 mass parts of packing in possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger and containing aliphatics ring type structure, add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1355.1 mass parts will be cooled to, 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 isocyanate group.
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; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (the IX) (equivalent weight of acryl: 2.50 * 10 4, weight-average molecular weight: 59000, non-volatile content: 25 quality %).
[comparative example 4]
Pack in possessing the four-hole boiling flask of 5 liters of thermometer, stirrer, rare gas element introducing port and reflux exchanger and make 1, the reaction of 4-butyleneglycol and hexanodioic acid and the polyester polyol (hydroxyl value: 112.2) 500.0 mass parts that obtains, add isophorone diisocyanate 222.2 mass parts, toluene 180.6 mass parts, reacted 3 hours under 80 ℃ on inhibition heat release limit, limit, thereby obtained having in molecular end the toluene solution of the carbamate prepolymer of isocyanate group.
Next, the above-mentioned toluene solution of 40 ℃, the N of 1444.6 mass parts will be cooled to, 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 isocyanate group.
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; reaction under 70 ℃ about 1 hour, thereby obtained acrylic modified urethane urea resin composition (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 modified urethane urea resin]
The weight-average molecular weight of the acrylic modified urethane urea resin that obtains in upper note embodiment and comparative example converts by the polystyrene standard that adopts gel permeation chromatography (GPC) and obtains.The solids component 0.4g of the acrylic modified urethane urea resin composition that obtains is dissolved in tetrahydrofuran (THF) 100g and makes the mensuration sample.
Determinator has used eastern groove (strain) high performance liquid chromatography HLC-8220 processed type.Chromatographic column is used in combination eastern Cao (strain) post TSK-GEL processed (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL).
As condition determination, column temperature is 40 ℃, and elutriant is tetrahydrofuran (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 above-described embodiment and comparative example, mix Irgacure184 (vapour bar 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 processes after 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 tetrahydrofuran (THF) (THF) under the environment of 23 ℃ of temperature and relative humidity 50%.
After above-mentioned dipping, above-mentioned test film is taken out from above-mentioned tetrahydrofuran (THF), estimate by visual shape to above-mentioned experimental film etc.
◎: experimental film keeps the shape before dipping, does not also produce pinprick, albefaction on its surface.
Zero: experimental film keeps the shape before dipping, but confirms to have pinprick, albefaction on its surface.
△: the part of experimental film (less than membrane area approximately 30%) dissolving.
*: the dissolving more than 50% of the total area of experimental film almost keeps the front film shape of dipping.
[stable on heating evaluation method]
Use Shimadzu 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 as follows: measure the beginning temperature: 40 ℃, heat-up rate: 3.0 ℃/minutes, 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
Polyisocyanates (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
Polyisocyanates 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 his-and-hers watches 1～2 describes.
(1,4 cyclohexane dimethanol is polycarbonate polyol, hydroxyl value to the UC-100 that " CH-PC " makes for the emerging product of space section (strain): 116.4).
" HG-PC " is that (1,6-hexylene glycol is polycarbonate polyol, hydroxyl value: 112.2) for " the ニ Star Port ラ Application 981 " of Japanese polyurethane industry (strain) system.
" BG-AA " polyester polyol (hydroxyl value: 112.2) for the reaction of BDO and hexanodioic acid is obtained.
" CH-AA " polyester polyol that contains aliphatics ring type structure (hydroxyl value: 112.2) for the reaction of 1,4 cyclohexane dimethanol and hexanodioic acid is obtained.
" IPDI " is isophorone diisocyanate.
" H12MDI " is HMDI.
" 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 industry
If acrylic modified urethane urea resin composition of the present invention, can form and have excellent solvent resistance and stable on heating molding, therefore can be used in the manufacturing such as the skin material of trolley part, household electrical appliances parts, wrapping material, film, sheet material, leather-like sheet etc.
In addition, acrylic modified urethane urea resin composition of the present invention can form and has excellent solvent resistance and stable on heating tunicle etc., therefore can be used in surface coated agent such as various base materials, tackiness agent etc.

Claims (10)

1. acrylic modified urethane urea resin composition, it is characterized in that, contain acrylic modified urethane urea resin (1) and solvent (2) forms, this acrylic modified urethane urea resin (1) is by making the polyvalent alcohol (A) that contains aliphatics ring type structure, the polyisocyanates (B) that contains aliphatics ring type structure, contain the polyamines (C) of aliphatics ring type structure and have acrylic compounds (D) reaction of the group that contains active hydrogen atom and obtain
Described polyvalent alcohol (A) has the hydroxyl value of 30～230mgKOH/g.
2. acrylic modified urethane urea resin composition as claimed in claim 1, wherein, in described acrylic modified urethane urea resin composition, mass ratio described acrylic modified urethane urea resin (1) and described solvent (2) is (1)/(2)=10～50/90～50.
3. acrylic modified urethane urea resin composition as claimed in claim 1 or 2; wherein, the equivalent weight from the acryl of described acrylic compounds (D) that has of described acrylic modified urethane urea resin is 10000～50000 scope.
4. acrylic modified urethane urea resin composition as claimed in claim 1 or 2, wherein, with respect to the polyvalent alcohol (A) that contains aliphatics ring type structure as the manufacturing raw material of described acrylic modified urethane urea resin described, contain aliphatics ring type structure polyisocyanates (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. acrylic modified urethane urea resin composition as claimed in claim 1 or 2, wherein, the described polyvalent alcohol (A) that contains aliphatics ring type structure for be selected from the polycarbonate polyol that contains aliphatics ring type structure and contain in the polyester polyol of aliphatics ring type structure more than a kind.
6. acrylic modified urethane urea resin composition as claimed in claim 5, wherein, the described polycarbonate polyol of aliphatics ring type structure that contains is by obtaining 1,4 cyclohexane dimethanol and carbonic ether and/or phosgene reaction.
7. acrylic modified urethane urea resin composition as claimed in claim 1 or 2, wherein, the described polyisocyanates (B) that contains aliphatics ring type structure be selected from HMDI and isophorone diisocyanate more than a kind.
8. acrylic modified urethane urea resin composition as claimed in claim 1 or 2, wherein, described (methyl) acrylic compounds (D) is for containing the alkyl acrylate of hydroxyl.
9. acrylic modified urethane urea resin composition as claimed in claim 1 or 2, wherein, described acrylic modified urethane urea resin (1) has 5000～200000 weight-average molecular weight.
10. molding, it obtains the described acrylic modified urethane urea resin composition moulding of any one in claim 1～9.
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