JP2011132548A - Film obtained by molding acrylic-modified urethane-urea resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film that achieves both excellent solvent resistance and heat resistance in a level which does not cause dissolution, deformation and discoloration or the like of the molding surface even when various solvents are attached. <P>SOLUTION: The film is obtained by molding an acrylic-modified urethane-urea resin composition containing an acrylic-modified urethane-urea resin (1) 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, and a solvent (2), wherein the alicyclic structure-containing polyol (A) is in the range of 40-80 mass% to the sum mass of the (A), (B), (C) and (D). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention The present invention relates to a film obtained by molding an acrylic-modified urethane urea resin composition.

  Molded articles obtained using urethane-based molding materials are currently used in various applications such as automobile parts, home appliance parts, packaging materials, and skin materials constituting leather-like sheets.

  The molded product is required to have various characteristics corresponding to its application. For example, when used for automobile interior and exterior materials, alcohol resistance and oleic acid resistance at a level that does not cause deformation or discoloration of the surface of the molded product due to adhesion of alcohol or oils and fats in foods, and high temperature environment in summer There is a case where heat resistance of a level that does not cause deformation or the like of a molded article when it is exposed to the bottom for a long time is required.

  Examples of the molding material that hardly causes deformation due to the alcohol as described above include, for example, a specific prepolymer obtained by reacting one or more of polytetramethylene carbonate diol and organic diisocyanate, and the prepolymer. An active group capable of reacting with an unreacted isocyanate at the end of the prepolymer at a molar ratio of the prepolymer / chain extender exceeding 1; A thermoplastic polyurethane molding material having a molecular weight of 3 to 200,000 and a gel percentage of 5% or less, which is terminated with a reaction stopper having one hydrogen, is known (for example, see Patent Document 1).

  However, a molded product obtained using the thermoplastic polyurethane molding material may not be practically sufficient in terms of heat resistance, and may cause deformation or the like when exposed to a high temperature environment for a long time. .

  On the other hand, in general, an adhesive is often used when the molded product is fixed to predetermined positions of various products. For example, when manufacturing automobile parts and household appliance parts, an organic solvent-type adhesive may be used for bonding members made of molded products having a predetermined shape.

  However, the organic solvent contained in the adhesive sometimes erodes the surface of the urethane-based molded product, and may cause dissolution, deformation, or discoloration of the surface of the molded product.

  In particular, when a film or sheet-like product is laminated as the molded product using an organic solvent-type adhesive, deformation such as dissolution or shrinkage of the film is caused by the influence of the organic solvent contained in the adhesive. And may cause discoloration.

  In this way, from the industry, even in such a case, molding capable of forming a molded product having a level of solvent resistance that does not cause dissolution, deformation, or discoloration of the surface of the molded product and the heat resistance. Development of materials is required.

  However, the molded product obtained by using the thermoplastic polyurethane molding material described in Patent Document 1 has good resistance to oil and fat components such as alcohol and oleic acid, but includes strong solvents. It is hard to say that it has sufficient solvent resistance against various organic solvents, but it is still difficult to prevent resin dissolution from the surface of the molded product, deformation of the molded product surface, discoloration, etc. due to adhesion of the solvent. There was a case.

  As described above, although a molded product having both excellent heat resistance and excellent solvent resistance against an organic solvent is strongly demanded from the industrial world, it has not been found yet.

JP 7-41540 A

The problem to be solved by the present invention is to achieve both excellent solvent resistance and heat resistance at a level that does not cause dissolution, deformation, or discoloration of the surface of the molded product even when various solvents adhere. Is to provide an improved film .

  The present inventors examined the introduction of an aliphatic cyclic structure into the urethane resin as described in Document 1 while proceeding with studies to solve the above problems. Specifically, combinations of various types of polyols and polyisocyanates were examined, and further, combinations with various types of chain extenders were also examined.

As a result, an acrylic-modified urethane urea resin obtained by reacting an aliphatic cyclic structure-containing polyol, an aliphatic cyclic structure-containing polyisocyanate, an aliphatic cyclic structure-containing polyamine, and an acrylic compound having an active hydrogen atom-containing group and only when the solvent is a film obtained by molding the acrylic-modified urethane urea resin composition containing, it found that can form a compatible and excellent solvent resistance and heat-resistant film.

That is, the present invention relates to an aliphatic cyclic structure-containing polyol (A), an aliphatic cyclic structure-containing polyisocyanate (B), an aliphatic cyclic structure-containing polyamine (C), and an acrylic compound having an active hydrogen atom-containing group ( obtained by reacting D) acryl-modified urethane urea resin (1) and solvent (2) Ri greens contain, the aliphatic cyclic structure-containing polyol (a) is an acrylic-modified urethane urea resin (1) Aliphatic cyclic structure-containing polyol (A), aliphatic cyclic structure-containing polyisocyanate (B), aliphatic cyclic structure-containing polyamine (C), and an acrylic having an active hydrogen atom-containing group. based on the total weight of the compound (D), obtained by molding the acrylic-modified urethane urea resin composition characterized scope der Rukoto 40-80 mass% off It relates to Lum.

Since the film obtained by molding the acrylic-modified urethane urea resin composition of the present invention can form a film having excellent solvent resistance and heat resistance, for example, automobile parts, home appliance parts, packaging materials, etc. It can be used for the production of skin materials for films, sheets and leather-like sheets.

  First, the acrylic-modified urethane urea resin (1) used in the present invention will be described.

  The acrylic-modified urethane urea resin (1) used in the present invention comprises an aliphatic cyclic structure-containing polyol (A), an aliphatic cyclic structure-containing polyisocyanate (B), an aliphatic cyclic structure-containing polyamine (C), and an activity. It is obtained by reacting with an acrylic compound (D) having a hydrogen atom-containing group.

The acrylic-modified urethane urea resin (1) must have an aliphatic cyclic structure in order to achieve excellent solvent resistance and heat resistance. It is important that the aliphatic cyclic structure is supplied from any of the aliphatic cyclic structure-containing polyol, the aliphatic cyclic structure-containing polyisocyanate, and the aliphatic cyclic structure-containing polyamine. For example, a resin using an aliphatic polyisocyanate instead of an aliphatic cyclic structure-containing polyisocyanate even if the mass ratio of the aliphatic cyclic structure present in the acrylic-modified urethane urea resin (1) is approximately the same. The composition may not be able to form a film with desired solvent resistance.

The acrylic-modified urethane urea resin (1) should have an aliphatic cyclic structure in the range of 20 to 60% by mass from the viewpoint of obtaining a film having both excellent solvent resistance and heat resistance. Is preferred. In addition, the mass ratio of the said aliphatic cyclic structure is the aliphatic cyclic structure containing polyol (A) which is a raw material used for manufacture of the said acrylic modified urethane urea resin (1), and an aliphatic cyclic structure containing polyisocyanate ( It is a ratio of the mass of the aliphatic cyclic structure in the raw material to the total mass of B), the aliphatic cyclic structure-containing polyamine (C), and the acrylic compound (D) having an active hydrogen atom-containing group.

  The acrylic-modified urethane urea resin (1) has a urethane bond and a urea bond. When a so-called urethane acrylate having no urea bond is used, the molding processability is low, and it may be difficult to produce a molded product such as a thin film. Therefore, as the acrylic modified urethane urea resin (1), a resin having 4 to 10% by mass of urea bond is used from the viewpoint of achieving both good heat resistance and solvent resistance as well as excellent moldability. Preferably, it is 5-8 mass%, It is more preferable that it is 6-7 mass%. In addition, the mass ratio of the urea bond is the aliphatic cyclic structure-containing polyol (A) and the aliphatic cyclic structure-containing polyisocyanate (B), which are raw materials used for the production of the acrylic-modified urethane urea resin (1). Is the ratio of the mass of the urea bond structure in the raw material to the total mass of the aliphatic cyclic structure-containing polyamine (C) and the acrylic compound (D) having an active hydrogen atom-containing group.

  In addition, as the acrylic-modified urethane urea resin (1), a resin having 5 to 15% by mass of a urethane bond is used from the viewpoint of achieving both good heat resistance and solvent resistance as well as excellent moldability. It is preferable to be 7 to 9% by mass. In addition, the mass ratio of the said urethane bond is the said aliphatic cyclic structure containing polyol (A) which is a raw material used for manufacture of the said acrylic modified urethane urea resin (1), and an aliphatic cyclic structure containing polyisocyanate (B). It is a ratio of the mass of the urethane bond structure in the raw material with respect to the total mass of the aliphatic cyclic structure-containing polyamine (C) and the acrylic compound (D) having an active hydrogen atom-containing group.

  The acrylic-modified urethane urea resin (1) preferably has a weight average molecular weight of 5,000 to 200,000 in order to maintain good moldability as well as excellent solvent resistance and heat resistance. A range of ˜200000 is more preferred. In addition, the weight average molecular weight of the said acrylic modified urethane urea resin (1) is the value calculated | required by styrene conversion, using a gel permeation chromatography (GPC) and using tetrahydrofuran as an eluent.

  The acrylic-modified urethane urea resin (1) used in the present invention has excellent solvent resistance and heat resistance when the equivalent weight of the acryloyl group derived from the acrylic compound (D) is in the range of 10,000 to 50,000. It is preferable in order to achieve both properties and 10000 to 30000 is more preferable. The equivalent weight of the acryloyl group refers to the aliphatic cyclic structure-containing polyol (A), the aliphatic cyclic structure-containing polyisocyanate (B) and the aliphatic cyclic that constitute the acrylic-modified urethane urea resin (1). The total mass of the structure-containing polyamine (C) and the acrylic compound (D) having an active hydrogen atom-containing group was divided by the equivalent of the acryloyl group derived from the acrylic compound (D) present in the acrylic-modified urethane urea resin. Points to the value.

  Next, the aliphatic cyclic structure-containing polyol (A) used for the production of the acrylic-modified urethane urea resin (1) will be described.

  As the aliphatic cyclic structure-containing polyol (A) used in the present invention, those having a hydroxyl value in the range of 30 to 230 mgKOH / g are preferably used, and those having a range of 50 to 230 mgKOH / g are used. More preferably. The hydroxyl value of the polyol (A) is a value measured according to JIS K0070.

  Examples of the aliphatic cyclic structure-containing polyol (A) include an aliphatic cyclic structure-containing polycarbonate polyol, an aliphatic cyclic structure-containing polyester polyol, an aliphatic cyclic structure-containing polyether polyol, and an aliphatic cyclic structure-containing acrylic. A polyol or the like can be used, and an aliphatic cyclic structure-containing diol is preferably used. Of these, from the viewpoint of achieving both excellent solvent resistance and heat resistance, it is more preferable to use an aliphatic cyclic structure-containing polycarbonate polyol and an aliphatic cyclic structure-containing polyester polyol, and an aliphatic cyclic structure. It is particularly preferred to use a polycarbonate diol containing and a polyester diol containing an aliphatic cyclic structure.

  The aliphatic cyclic structure-containing polycarbonate polyol is obtained, for example, by reacting a carbonate ester and / or phosgene with a relatively low molecular weight aliphatic cyclic structure-containing polyol (a1) of about 50 to 400 described later. Can be used.

  As the carbonate ester, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the aliphatic cyclic structure-containing polyol (a1) capable of reacting with the carbonate ester or phosgene include 1,2-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclohexane Octanediol, 1,4-cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,0,2,6] decane-dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol , Tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1 , 1] dodecanol, spiro [3,4] octanediol, bu Cyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, hydrogenated bisphenol A, 1,3-adamantanediol, etc. can be used, among which 1,4-cyclohexanedimethanol is used It is preferable to do.

  Examples of the aliphatic cyclic structure-containing polyester polyol include those obtained by reacting an aliphatic cyclic structure-containing polyol having a relatively low molecular weight of about 50 to 400 with a polycarboxylic acid, or a low molecular polyol and a fat. Use can be obtained by reacting with a polycarboxylic acid containing an aromatic ring structure, or can be obtained by adding a cyclic ester compound such as ε-caprolactone or γ-valerolactone to a part of them by ring-opening polymerization reaction. can do.

  Examples of the aliphatic cyclic structure-containing polyol that can be used for the production of the aliphatic cyclic structure-containing polyester polyol include the aliphatic cyclic structure-containing polyols exemplified as those that can be used for the production of the aliphatic cyclic structure-containing polycarbonate polyol. The same as (a1) can be used.

  Examples of the polycarboxylic acid capable of reacting with the low molecular weight aliphatic cyclic structure-containing polyol include, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and dimer acid aliphatic polycarboxylic acid. Acid, aliphatic cyclic structure-containing polycarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and cyclohexanetricarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, Aromatic polycarboxylic acids such as 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimellitic acid and pyromellitic acid, and anhydrides or ester derivatives thereof can be used alone or in combination of two or more thereof. It is preferable to use an aliphatic polycarboxylic acid.

  As the aliphatic cyclic structure-containing polycarboxylic acid that can be used in the production of the aliphatic cyclic structure-containing polyester polyol, 1,4-cyclohexanedicarboxylic acid and the like can be used as described above.

  Examples of the polyol that can be used for the reaction with the aliphatic cyclic structure-containing polycarboxylic acid include, in addition to the aliphatic cyclic structure-containing polyol (a1), for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1 , 10-decanediol, 1,11-undecanediol, 1,12- Decanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1, Aliphatic polyols such as 3-hexanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, ditrimethylolpropane, tritrimethylolpropane, and pentaerythritol can be used.

  As the aliphatic cyclic structure-containing polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  As the initiator, for example, the same aliphatic cyclic structure-containing polyol (a1) as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanedimethanol and the like can be used. If necessary, conventionally known ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl Aliphatic polyols such as glycol, glycerin, trimethylolethane and trimethylolpropane can be used in combination.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

Examples of the aliphatic cyclic structure-containing polyol (A) include the aliphatic cyclic structure-containing polycarbonate polyol, the aliphatic cyclic structure-containing polyester polyol, the aliphatic cyclic structure-containing polyether polyol, and the like. It is preferable to use an active hydrogen-containing chain extender in combination because a film excellent in solvent resistance, heat resistance and durability can be formed.

  Examples of the other active hydrogen-containing chain extender include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 3,3′-dimethylol heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis (hydroxymethyl) heptane, diethylene glycol, diethylene glycol Polyhydric alcohols such as propylene glycol, glycerin, trimethylolpropane, sorbitol and hydroquinone diethylol ether can be used alone or in combination of two or more.

  In the present invention, in addition to the aliphatic cyclic structure-containing polyol (A), if necessary, conventionally known aliphatic polycarbonate polyol, aromatic polycarbonate polyol, aliphatic polyester polyol, aromatic polyester polyol, aliphatic Other polyols such as polyether polyol and aromatic polyether polyol can be used in combination.

The aliphatic cyclic structure-containing polyol (A) is an aliphatic cyclic structure-containing polyol (A) that is a raw material used for the production of the acrylic-modified urethane urea resin (1) of the present invention. It is essential to use in the range of 40 to 80% by mass with respect to the total mass of the isocyanate (B), the aliphatic cyclic structure-containing polyamine (C) and the acrylic compound (D).

Next, the aliphatic cyclic structure-containing polyisocyanate (B) will be described.
Examples of the aliphatic cyclic structure-containing polyisocyanate (B) include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-methylcyclohexane diisocyanate, cyclohexylene diisocyanate, and methylcyclohexylene. Use diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane diisocyanate, dimer acid diisocyanate, bicycloheptane triisocyanate, etc. be able to. Of these, diisocyanate is preferably used from the viewpoint of imparting excellent solvent resistance and heat resistance to the molded article of the present invention, more preferably isophorone diisocyanate or 4,4′-dicyclohexylmethane diisocyanate. It is particularly preferred to use 4,4'-dicyclohexylmethane diisocyanate.

  In the present invention, in addition to the aliphatic cyclic structure-containing polyisocyanate (B), if necessary, aromatic polyisocyanates such as phenylene diisocyanate and tolylene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate. Other polyisocyanates such as can be used in combination.

  The aliphatic cyclic structure-containing polyisocyanate (B) includes an aliphatic cyclic structure-containing polyol (A) and an aliphatic cyclic structure-containing poly, which are raw materials used for producing the resulting acrylic-modified urethane urea resin (1). It is preferable to use in 15-50 mass% with respect to the total mass of isocyanate (B), an aliphatic cyclic structure containing polyamine (C), and an acrylic compound (D).

  Next, the aliphatic cyclic structure-containing polyamine (C) will be described.

  The aliphatic cyclic structure-containing polyamine (C) is used for introducing a urea bond into the acrylic-modified urethane urea resin.

As the aliphatic cyclic structure-containing polyamine (C), for example, isophorone diamine, 4,4′-dicyclohexylmethane diamine, diaminocyclohexane, methyldiaminocyclohexane, biperazine, norbornene diamine, and the like can be used. In particular, it is preferable to use isophoronediamine and 4,4′-dicyclohexylmethanediamine for forming a film excellent in heat resistance and solvent resistance.

  Moreover, in this invention, the aliphatic polyamine conventionally known as chain extenders, such as ethylenediamine other than the said aliphatic cyclic structure containing polyamine (C), as needed, does not impair the effect of this invention. You may use together in the range.

  The aliphatic cyclic structure-containing polyamine (C) is an aliphatic cyclic structure-containing polyol (A) and an aliphatic cyclic structure-containing polyisocyanate that are raw materials used for the production of the resulting acrylic-modified urethane urea resin (1). It is preferable to use in the range of 1-20 mass% with respect to the total mass of (B), an aliphatic cyclic structure containing polyamine (C), and an acrylic compound (D).

  Next, the acrylic compound (D) having the active hydrogen atom-containing group will be described.

  The acrylic compound (D) having an active hydrogen atom-containing group used in the present invention is used for introducing an acryloyl group into the acrylic-modified urethane urea resin, and is an active hydrogen atom that can react with an isocyanate group. The one having a containing group is used.

  Examples of the active hydrogen atom-containing group include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferable.

  As said acrylic compound (D), the acrylic compound which has the said hydroxyl group, the acrylic compound which has a carboxyl group, etc. can be used, However, It is preferable to use the acrylic compound which has a hydroxyl group.

  Examples of the acrylic compound having a hydroxyl group include hydroxyl group-containing acrylics such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Acid alkyl esters, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and the like can be used. Among these, from the viewpoint of solvent resistance and heat resistance, it is preferable to use a hydroxyl group-containing acrylic acid alkyl ester, and from the viewpoint of easy availability of raw materials, 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate should be used. preferable.

  The acrylic compound (D) includes an aliphatic cyclic structure-containing polyol (A), an aliphatic cyclic structure-containing polyisocyanate (B), and an aliphatic ring, which are raw materials used for the production of the acrylic-modified urethane urea resin (1). It is preferable to use in the range of 0.05-10 mass% with respect to the total mass of a formula structure containing polyamine (C) and an acrylic compound (D).

  Further, a part of the acrylic compound (D) may be present in an unreacted state in the acrylic-modified urethane urea resin composition of the present invention. That is, the acrylic modified urethane urea resin composition of the present invention may contain the unreacted acrylic compound (D) together with the acrylic modified urethane urea resin.

  Next, the solvent (2) used in the present invention will be described.

  As the solvent (2), an organic solvent and an aqueous solvent can be used, but it is more preferable to use an organic solvent from the viewpoint of further improving the moldability of the molded product.

  When the organic solvent is used as the solvent (2), it is not particularly limited. For example, ethyl acetate, butyl acetate, ethyl lactate, cellosolve, cellosolve acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, dimethyl Formamide, dimethylacetamide, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, methanol, isopropanol, 2-butanol, n-butanol, isopropyl alcohol, ethylene glycol monomethyl ether Acetate or the like can be used, and these may be used alone or in combination. Moreover, these organic solvents are suitably selected according to the use used.

  Moreover, the mass ratio of the said acrylic modified urethane urea resin (1) and the said solvent (2) in the acrylic modified urethane urea resin composition of this invention is (1) / (2) = 10-50 / 90-50. It is essential that it is in the range of 15 to 35/85 to 65.

  Next, the manufacturing method of the said acrylic modified urethane urea resin (1) is demonstrated.

  As a manufacturing method of the said acrylic modified urethane urea resin (1), the method of the following manufacturing method (i)-manufacturing method (ii) is mentioned, for example. Among these, the production by the following method (i) is preferable because the reaction can be easily controlled.

  In the production method (i), the aliphatic cyclic structure-containing polyol (A), the aliphatic cyclic structure-containing polyisocyanate (B), and, if necessary, the other active hydrogen under the solvent (2). A urethane prepolymer having an isocyanate group at the molecular end is obtained by reacting with the chain extender contained, and then the urethane prepolymer, the aliphatic cyclic structure-containing polyamine (C), and the acrylic compound (D) This is a method for producing an acrylic-modified urethane urea resin (1) by reacting.

  The reaction between the aliphatic cyclic structure-containing polyol (A) and the aliphatic cyclic structure-containing polyisocyanate (B) includes the hydroxyl group and aliphatic cyclic structure contained in the aliphatic cyclic structure-containing polyol (A). The equivalent ratio [isocyanate group / hydroxyl group] to the isocyanate group of the polyisocyanate (B) is preferably 1.1 / 1.0 to 5.0 / 1.0, preferably 1.5 / 1.0. More preferably, it is in the range of -3.0 / 1.0. The reaction between the aliphatic cyclic structure-containing polyol (A) and the aliphatic cyclic structure-containing polyisocyanate (B) is preferably carried out at a temperature of 20 to 120 ° C. for about 30 minutes to 24 hours. .

  The urethane prepolymer having an isocyanate group at the molecular end obtained by the reaction of the aliphatic cyclic structure-containing polyol (A) and the aliphatic cyclic structure-containing polyisocyanate (B), and the aliphatic cyclic structure The reaction between the containing polyamine (C) and the acrylic compound (D) is, for example, a urethane urea prepolymer obtained by supplying and reacting the urethane prepolymer and the aliphatic cyclic structure-containing polyamine (C) all together or sequentially. Acrylic-modified urethane urea resin (1) can be produced by reacting the urethane urea prepolymer with the acrylic compound (D). At that time, the equivalent ratio [amino group / isocyanate group] of the isocyanate group of the urethane prepolymer and the amino group of the aliphatic cyclic structure-containing polyamine (C) is 0.70 / 1.0 to 0.99 / A range of 1.0 is preferred. In addition, the urethane prepolymer, the aliphatic cyclic structure-containing polyamine (C), and the acrylic compound (D) are mixed together or sequentially and allowed to react for approximately 1 to 3 hours at 20 to 80 ° C. Can also be manufactured.

  Moreover, the said manufacturing method (ii) makes the molecular terminal by reacting the said aliphatic cyclic structure containing polyisocyanate (B) and the said aliphatic cyclic structure containing polyamine (C) under the said solvent (2). An isocyanate group-containing polyurea prepolymer is obtained, and then the polyurea prepolymer, the aliphatic cyclic structure-containing polyol (A), the acrylic compound (D), and, if necessary, the other active hydrogen-containing chain. This is a method for producing an acrylic-modified urethane urea resin (1) by reacting with an extender.

  The reaction between the aliphatic cyclic structure-containing polyisocyanate (B) and the aliphatic cyclic structure-containing polyamine (C) is carried out by reacting the isocyanate group of the aliphatic cyclic structure-containing polyisocyanate (B) with the aliphatic ring. It is preferable that the equivalent ratio [isocyanate group / amino group] of the amino group of the formula structure-containing polyamine (C) is 1.1 / 1.0 to 5.0 / 1.0. The reaction between the aliphatic cyclic structure-containing polyisocyanate (B) and the aliphatic cyclic structure-containing polyamine (C) is preferably carried out at a temperature of 20 to 80 ° C. for about 30 minutes to 1 hour. .

  A polyurea prepolymer having an isocyanate group at the molecular end obtained by the reaction of the aliphatic cyclic structure-containing polyisocyanate (B) and the aliphatic cyclic structure-containing polyamine (C); and the aliphatic cyclic structure. The reaction between the structure-containing polyol (A) and the acrylic compound (D) can be achieved by, for example, supplying the polyurea prepolymer and the aliphatic cyclic structure-containing polyol (A) together or sequentially and reacting them. An acrylic modified urethane urea resin (1) can be produced by producing a urethane urea prepolymer having an isocyanate group and reacting the urethane urea prepolymer with the acrylic compound (D). Moreover, it can also manufacture by making the said polyurea prepolymer, the said aliphatic cyclic structure containing polyol (A), and the said acrylic compound (D) react collectively and sequentially.

  When producing the acrylic-modified urethane urea resin (1), a tertiary amine catalyst or an organometallic catalyst is used as necessary in any of the production methods (i) and (ii). To promote the reaction.

Contains acrylic modified urethane urea resin (1) and solvent (2) obtained by the above method The acrylic-modified urethane urea resin composition may contain a curing agent and a curing accelerator as necessary.

  As said hardening | curing agent, photocuring agents, such as a ultraviolet curing agent and an electron beam hardening agent, and a thermosetting agent can be used, for example.

  The ultraviolet curing agent is a photosensitizer, for example, a benzoin ether type such as benzoin alkyl ether; a benzophenone type such as benzophenone or methyl orthobenzoyl benzoate; benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy Acetophenones such as 2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone; 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Thioxanthone compounds can be used.

  As said electron beam hardening | curing agent, halogenated alkylbenzene, a disulfide type compound, etc. can be used, for example.

  As other photocuring agents, for example, hydroxyalkylphenone compounds, alkylthioxanthone compounds, sulfonium salt compounds, and the like can be used.

  As the thermosetting agent, an organic peroxide can be used. Specifically, a diacyl peroxide system, a peroxy ester system, a hydroperoxide system, a dialkyl peroxide system, a ketone peroxide system, a peroxy compound can be used. Ketal-based, alkyl perester-based, percarbonate-based compounds and the like can be used.

  Although the usage-amount of the said hardening | curing agent changes with kinds to be used, it is preferable to use normally in the range of 0.1-10 mass parts with respect to 100 mass parts of said acrylic modified urethane urea resins (1). It is more preferable to use in the range of ˜5 parts by mass.

  Moreover, as said hardening accelerator, organic metal salts, such as cobalt naphthenate and cobalt octenoate, amine type, (beta) -diketone, etc. can be used, for example.

Acrylic modified urethane urea resin composition used in the present invention, in addition to those mentioned above, within the range not impairing the effects of the present invention may contain other additives.

  Examples of the other additives include, for example, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl from the viewpoint of preventing termination of radical polymerization due to the influence of oxygen in the atmosphere. An allyl ether compound of polyhydric alcohols such as ether, 1,2-butylene glycol monoallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, pentaerythritol triallyl ether, and the like can also be used.

Moreover, as said other additive, an acrylic compound can be used from a viewpoint of improving the heat resistance and durability of the film obtained.

  Examples of the acrylic compound include those similar to those exemplified as the acrylic compound (D), 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and ethylene glycol diester. (Meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri Polyfunctional acrylic compounds such as methylolpropane tri (meth) acrylate can be used.

  Examples of the other additives include fillers, pigments, dyes, surfactants, antistatic agents, ultraviolet absorbers, polymerization inhibitors, adhesion-imparting agents, plasticizers, antioxidants, leveling agents, Various conventionally known additives such as film forming aids, stabilizers, flame retardants and the like can be used as long as the effects of the present invention are not impaired.

The method for curing the acrylic-modified urethane urea resin composition used in the present invention differs depending on the kind of the curing agent described above. For example, the acrylic-modified urethane urea resin composition using the ultraviolet curing agent can be cured by irradiating predetermined ultraviolet rays using a general ultraviolet light irradiation device such as a metal halide lamp, a mercury lamp, or an ultraviolet LED lamp. it can. On the other hand, the acrylic-modified urethane urea resin composition using the thermosetting agent can be cured by heating at a temperature of preferably 50 to 250 ° C. using, for example, a high-temperature furnace.

Film using the acrylic-modified urethane urea resin composition As a method for producing, for example, the acrylic modified urethane urea resin composition on the surface of a release substrate, for example, a slit coater method such as a curtain flow coater method or a die coater method, a knife coater method, a roll coater method, a slit coater method Specifically, a method of coating by a die coater method or the like, drying as necessary, and then irradiating or heating with ultraviolet rays or the like and curing is preferable.

The film obtained by the above method is excellent in solvent resistance and heat resistance. For example, molded products such as counters and bathtubs, building members, automobile parts, home appliance parts, medical instrument parts, various containers, and packaging applications. It can be used in various applications such as a film or sheet for forming a skin layer or intermediate layer of a leather-like sheet.

  Further, when the acrylic-modified urethane urea resin composition is used as a coating agent or an adhesive, as a method for applying them to various substrate surfaces, for example, a slit coater method such as a curtain flow coater method or a die coater method, a knife Examples thereof include a coater method and a roll coater method.

  After coating by the above method, the solvent is dried if necessary and the curing proceeds, as described above, depending on the type of the curing agent to be used, by heating or irradiating with ultraviolet rays or the like, the film or adhesive layer Can be formed. In addition, although the said drying may be natural drying at normal temperature, it can also be heat-dried. The heat drying is usually preferably performed at 40 to 250 ° C. for about 1 to 600 seconds.

  Since the coating film and adhesive layer formed by the above method are also excellent in the solvent resistance and heat resistance, for example, for surface coating and adhesion of various substrates such as metal substrates, plastic substrates, and wood substrates. It is possible to use.

[ Synthesis Example 1]
An aliphatic cyclic structure-containing polycarbonate polyol (UC-100, manufactured by Ube Industries, Ltd., hydroxyl value) was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 116.4) Charge 500.0 parts by mass, add 222.2 parts by mass of isophorone diisocyanate, 180.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation, so that an isocyanate group is added to the molecular terminal. A toluene solution of a urethane prepolymer having the following was obtained.

  Next, the toluene solution cooled to 40 ° C., 1447.2 parts by mass of N, N-dimethylformamide, and 543.1 parts by mass of toluene were mixed, and then mixed with 73.6 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 8.1 parts by mass of 2-hydroxyethyl acrylate and 241.2 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. Urea resin composition (I) (equivalent weight of acryloyl group; 1.15 × 10 ⁴ , weight average molecular weight; 21000, nonvolatile content; 25% by mass) was obtained.

[ Synthesis Example 2]
An aliphatic cyclic structure-containing polycarbonate polyol (UC-100, manufactured by Ube Industries, Ltd., hydroxyl value) was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 116.4) Charge 500.0 parts by mass, add 222.2 parts by mass of isophorone diisocyanate, 180.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation, so that an isocyanate group is added to the molecular terminal. A toluene solution of a urethane prepolymer having the following was obtained.

  Next, the toluene solution cooled to 40 ° C., 1445.9 parts by mass of N, N-dimethylformamide, and 542.4 parts by mass of toluene were mixed, and then mixed with 75.2 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 5.8 parts by mass of 2-hydroxyethyl acrylate, and 241.0 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. Urea resin composition (II) (equivalent weight of acryloyl group; 1.61 × 10 ⁴ , weight average molecular weight; 39000, nonvolatile content; 25% by mass) was obtained.

[ Synthesis Example 3]
An aliphatic cyclic structure-containing polycarbonate polyol (UC-100, manufactured by Ube Industries, Ltd., hydroxyl value) was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 116.4) Charge 500.0 parts by mass, add 222.2 parts by mass of isophorone diisocyanate, 180.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation, so that an isocyanate group is added to the molecular terminal. A toluene solution of a urethane prepolymer having the following was obtained.

  Next, the toluene solution cooled to 40 ° C., 1444.6 parts by mass of N, N-dimethylformamide, and 541.7 parts by mass of toluene were mixed, and then mixed with 76.8 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate, and 240.8 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. Urea resin composition (III) (equivalent weight of acryloyl group; 2.66 × 10 ⁴ , weight average molecular weight; 64000, nonvolatile content; 25% by mass) was obtained.

[ Synthesis Example 4]
An aliphatic cyclic structure-containing polycarbonate polyol (UC-100, manufactured by Ube Industries, Ltd., hydroxyl value) was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 116.4) Charge 500.0 parts by mass, add 262.4 parts by mass of 4,4′-dicyclohexylmethane diisocyanate and 190.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation. Thus, a toluene solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, the toluene solution cooled to 40 ° C., 1516.8 parts by mass of N, N-dimethylformamide, and 567.8 parts by mass of toluene were mixed, and then mixed with 76.8 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate and 252.8 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. Urea resin composition (IV) (equivalent weight of acryloyl group; 2.80 × 10 ⁴ , weight average molecular weight; 128000, nonvolatile content; 25% by mass) was obtained.

[ Synthesis Example 5]
An aliphatic cyclic structure-containing polycarbonate polyol (UC-100, manufactured by Ube Industries, Ltd., hydroxyl value) was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 116.4) Charge 500.0 parts by mass, add 262.4 parts by mass of 4,4′-dicyclohexylmethane diisocyanate and 190.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation. Thus, a toluene solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, the toluene solution cooled to 40 ° C., 1549.3 parts by mass of N, N-dimethylformamide, and 584.1 parts by mass of toluene were mixed, and then 94. 4 of 4,4′-dicyclohexylmethanediamine. A urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained by mixing with 9 parts by mass and reacting at 60 ° C. for 3 hours.

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate, and 258.2 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. A urea resin composition (V) (equivalent weight of acryloyl group; 2.86 × 10 ⁴ , weight average molecular weight; 172000, nonvolatile content; 25% by mass) was obtained.

[ Synthesis Example 6]
Aliphatic cyclic structure obtained by reacting 1,4-cyclohexanedimethanol and adipic acid in a 5-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser Containing polyester polyol (hydroxyl value: 112.2) 500.0 parts by mass, adding 262.4 parts by mass of 4,4′-dicyclohexylmethane diisocyanate and 190.6 parts by mass of toluene, By reacting at 3 ° C. for 3 hours, a toluene solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, the toluene solution cooled to 40 ° C., 1516.8 parts by mass of N, N-dimethylformamide, and 567.8 parts by mass of toluene were mixed, and then mixed with 76.8 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate and 252.8 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. Urea resin composition (VI) (equivalent weight of acryloyl group; 2.80 × 10 ⁴ , weight average molecular weight; 157000, nonvolatile content: 25% by mass) was obtained.

[Comparative Synthesis Example 1]
An aliphatic cyclic structure-containing polycarbonate polyol (UC-100, manufactured by Ube Industries, Ltd., hydroxyl value) was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 116.4) Charge 500.0 parts by mass, add 222.2 parts by mass of isophorone diisocyanate, 180.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation, so that an isocyanate group is added to the molecular terminal. A toluene solution of a urethane prepolymer having the following was obtained.

  Next, the toluene solution cooled to 40 ° C., 1442.6 parts by mass of N, N-dimethylformamide, and 540.7 parts by mass of toluene were mixed, and then mixed with 79.2 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

  Next, the urethane urea prepolymer solution and 240.4 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby the urethane urea resin composition (VII) (equivalent weight of acryloyl group; -, Weight average molecular weight; 70000, non-volatile content; 25% by mass).

[Comparative Synthesis Example 2]
To a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, a 1,6-hexanediol-based polycarbonate polyol (“Nipporan 981” manufactured by Nippon Polyurethane Industry Co., Ltd.) Hydroxyl value: 112.2) 500.0 parts by mass were charged, 222.2 parts by mass of isophorone diisocyanate and 180.6 parts by mass of toluene were added, and the reaction was allowed to proceed at 80 ° C. for 3 hours while suppressing heat generation. A toluene solution of a urethane prepolymer having an isocyanate group was obtained.

  Next, the toluene solution cooled to 40 ° C., 1444.6 parts by mass of N, N-dimethylformamide, and 541.7 parts by mass of toluene were mixed, and then mixed with 76.8 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate, and 240.8 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. A urea resin composition (VIII) (equivalent weight of acryloyl group; 2.66 × 10 ⁴ , weight average molecular weight; 61000, nonvolatile content; 25% by mass) was obtained.

[Comparative Synthesis Example 3]
An aliphatic cyclic structure-containing polycarbonate polyol (UC-100, manufactured by Ube Industries, Ltd., hydroxyl value) was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 116.4) Charge 500.0 parts by mass, add 222.2 parts by mass of isophorone diisocyanate, 180.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation, so that an isocyanate group is added to the molecular terminal. A toluene solution of a urethane prepolymer having the following was obtained.

  Next, the toluene solution cooled to 40 ° C., 1355.1 parts by mass of N, N-dimethylformamide, and 497.0 parts by mass of toluene were mixed, and then mixed with 27.1 parts by mass of ethylenediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate, and 225.8 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. Urea resin composition (IX) (equivalent weight of acryloyl group; 2.50 × 10 ⁴ , weight average molecular weight; 59000, nonvolatile content; 25% by mass) was obtained.

[Comparative Synthesis Example 4]
Polyester polyol (hydroxyl value: obtained by reacting 1,4-butanediol and adipic acid with a 5-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 112.2) Preparation of 500.0 parts by mass, addition of 222.2 parts by mass of isophorone diisocyanate and 180.6 parts by mass of toluene, and reaction at 80 ° C. for 3 hours while suppressing heat generation, resulted in an isocyanate group at the molecular end. A toluene solution of a urethane prepolymer having the following was obtained.

  Next, the toluene solution cooled to 40 ° C., 1444.6 parts by mass of N, N-dimethylformamide, and 541.7 parts by mass of toluene were mixed, and then mixed with 76.8 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate, and 240.8 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. Urea resin composition (X) (equivalent weight of acryloyl group; 2.66 × 10 ⁴ , weight average molecular weight; 64000, nonvolatile content; 25% by mass) was obtained.

[Method for measuring weight average molecular weight of acrylic-modified urethane urea resin]
The weight average molecular weights of the acrylic modified urethane urea resins obtained in the above Examples and Comparative Examples were determined by standard polystyrene conversion by gel permeation chromatography (GPC). A 0.4 g solid content of the resulting acrylic-modified urethane urea resin composition was dissolved in 100 g of tetrahydrofuran to prepare a measurement sample.
The measuring device used was a high performance liquid chromatograph HLC-8220 manufactured by Tosoh Corporation. As a column, Tosoh Corporation column TSK-GEL (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL) was used in combination.
As measurement conditions, the column temperature was 40 ° C., the eluent was tetrahydrofuran, the flow rate was 1.0 mL / min, the sample injection amount was 500 μL, and the standard polystyrene was TSK standard polystyrene.

[Examples 1-6, Comparative Examples 1-4]
[Method for producing molded product (film)]
2 parts by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd., photopolymerization initiator) is mixed with 100 parts by mass of the solid content of the resin composition obtained in the above synthesis examples and comparative synthesis examples, and stirred for 10 minutes. Thus, a coating solution was obtained.

The coating solution was coated on a polyethylene terephthalate film that had been subjected to a release treatment, and then dried at 100 ° C. for 20 minutes using a hot air dryer, and then a conveyor type ultraviolet irradiation device (GS A film having a thickness of 50 μm after curing was obtained by irradiating 1000 mJ / cm ² using CSOT-40) manufactured by Yuasa Corporation.

[Evaluation method of solvent resistance]
A test film was obtained by cutting the film prepared by the above method into a size of 50 mm long × 50 mm wide. Subsequently, what fixed the said test film so that tension might not be applied to the frame whose inner dimension is 40 mm long x 40 mm wide was made into the test piece.

  Next, the test piece was immersed in tetrahydrofuran (THF) for 1 minute in an environment at a temperature of 23 ° C. and a relative humidity of 50%.

  After the immersion, the test piece was taken out from the tetrahydrofuran, and the shape and the like of the test film were visually evaluated.

  A: The test film retained the shape before immersion, and no pinholes or whitening occurred on the surface.

  ○: Although the test film retained the shape before immersion, pinholes and whitening were confirmed on the surface.

  Δ: Part of the test film (less than about 30% of the film area) was dissolved.

  X: 50% or more of the total area of the test film was dissolved, and the film shape before immersion was hardly retained.

[Evaluation method of heat resistance]
Using the Shimadzu flow tester CFT500D-1 (manufactured by Shimadzu Corporation), the flow starting temperature of the film prepared by the above method is 40 ° C., the heating rate: 3.0 ° C./min, the heating method, Measurement was performed under the conditions of cylinder pressure: 9.807 × 10 ⁵ Pa, die: 1 mm × 1 mmL, load: 98 N, hold time: 600 seconds.

  Those having a flow start temperature of approximately 180 ° C. or higher were evaluated as having excellent heat resistance.

Abbreviations in Tables 1 and 2 will be described.
“CH-PC” is UC-100 (1,4-cyclohexanedimethanol-based polycarbonate polyol, hydroxyl value: 116.4) manufactured by Ube Industries, Ltd.
“HG-PC” is “Nipporan 981” (1,6-hexanediol-based polycarbonate polyol, hydroxyl value: 112.2) manufactured by Nippon Polyurethane Industry Co., Ltd.
“BG-AA” is a polyester polyol (hydroxyl value: 112.2) obtained by reacting 1,4-butanediol and adipic acid.
“CH-AA” is an aliphatic cyclic structure-containing polyester polyol (hydroxyl value: 112.2) obtained by reacting 1,4-cyclohexanedimethanol and adipic acid.
“IPDI” is isophorone diisocyanate.
“H12MDI” is 4,4′-dicyclohexylmethane diisocyanate.
“IPDA” is isophoronediamine.
“EDA” is ethylenediamine.
“H12MDA” is 4,4′-dicyclohexylmethanediamine.
“HEA” is 2-hydroxyethyl acrylate.

  Since the acrylic-modified urethane urea resin composition of the present invention can form a molded product having excellent solvent resistance and heat resistance, for example, automobile parts, home appliance parts, packaging materials, films and sheets, leather-like It can be used for the manufacture of sheet skin materials and the like.

Claims (5)

Reacting an aliphatic cyclic structure-containing polyol (A), an aliphatic cyclic structure-containing polyisocyanate (B), an aliphatic cyclic structure-containing polyamine (C), and an acrylic compound (D) having an active hydrogen atom-containing group. raw Ri Na contain acrylic-modified urethane urea resin obtained (1) and solvent (2), the aliphatic cyclic structure-containing polyol (a) is used to make the acrylic-modified urethane urea resin (1) by An aliphatic cyclic structure-containing polyol (A), an aliphatic cyclic structure-containing polyisocyanate (B), an aliphatic cyclic structure-containing polyamine (C), and an acrylic compound (D) having an active hydrogen atom-containing group. based on the total weight, it was obtained by molding the acrylic-modified urethane urea resin composition characterized scope der Rukoto 40-80 wt% film. The mass ratio of the acrylic modified urethane urea resin (1) and the solvent (2) in the acrylic modified urethane urea resin composition is (1) / (2) = 10-50 / 90-50. A film obtained by molding the acrylic-modified urethane urea resin composition according to 1. It is obtained by molding the acrylic modified urethane urea resin composition according to claim 1 or 2, wherein an equivalent weight of the acryloyl group derived from the acrylic compound (D) of the acrylic modified urethane urea resin is in the range of 10,000 to 50,000. Film . The aliphatic cyclic structure-containing polyol (A), the aliphatic cyclic structure-containing polyisocyanate (B), the aliphatic cyclic structure-containing polyamine (C), and the active hydrogen atom-containing, which are raw materials for producing the acrylic-modified urethane urea resin weight ratio of aliphatic cyclic structure with respect to the total weight of the acrylic compound having a group (D) is 20 to 60 wt%, the acrylic-modified urethane urea resin composition according to any one of claims 1 to 3 Film obtained by molding . The aliphatic cyclic structure-containing polyol (A) and the aliphatic cyclic structure-containing polyisocyanate (B), wherein the acrylic-modified urethane urea resin (1) is a raw material used for the production of the acrylic-modified urethane urea resin (1) ), An aliphatic cyclic structure-containing polyamine (C), and an acrylic compound (D) having an active hydrogen atom-containing group, the mass ratio of the urea bond structure in the raw material is 4 to 10% by mass. The film obtained by shape | molding the acrylic modified urethane urea resin composition of any one of Claims 1-4 .