CN107207901A - Coating urethane resin compositions and the feel coating using said composition - Google Patents

Abstract

First, in order to provide the coating urethane resin compositions and feel coating composition of the feel for taking into account the chemical proofing to ultra-violet absorber etc., durability and softness, it will make that at least there is the polyalcohol of a range of hydroxy functional group number and coating urethane resin compositions obtained from general polyisocyanates reaction to be used for coating material.Second; in order to provide the low-temperature bending of cured film for possessing sufficient operating characteristics and low temperature fluidity and being formed, grip, water resistance, heat resistance also excellent active energy ray-curable resin composition; there is provided following compositions, wherein polyalcohol is that the PCDL comprising specific construction unit, (methyl) acrylate include more than 1 hydroxyl and more than 1 (methyl) acryloyl group.

Description

Coating urethane resin compositions and the feel coating using said composition

Technical field

Combined the present invention relates to the coating containing polyisocyanates, special polyol and delustering agent with carbamate resins Thing and the feel coating and actinic energy ray curable resion composition using said composition.

Background technology

Abrasion performance, bendability, flexibility, flexibility, processability, cementability, chemical proofing of polyurethane resin etc. Each physical properties excellent, and also excellent to the adaptability of various processing methods, therefore, as electronic device member, clothes, furniture, household electrical appliances, Sundry goods, the building resin component such as building and coating material, ink, bonding agent, coating on automobile component or as thin The various formed bodies such as film, sheet material and be widely used.As the polyol component reacted with isocyanates, polyether polyols have been used Alcohol, PEPA.And then, in recent years, high for hydrolytic resistance, heat resistance, abrasion performance, chemical proofing etc. is wanted Ask, it is proposed that use PCDL (patent document 1).However, being on the one hand directed to soft (soft feel) sense of touch The expectation of coating, as hard feel, therefore, in order to obtain durability and soft sense of touch, it is also proposed that use specific structure PCDL (patent document 2).

In addition, the carbamate resins containing unsaturated group are imbued with flexibility, can form tough cured film, because This, it is wide in ink, coating, bonding agent, smears, surface conditioning agent as active energy ray curable resin It is general to use.

Typically, the carbamate resins containing unsaturated group are to make polyol component, isocyanate prepolymer composition and free radical Obtained from the hydroxyl unsaturated monomer composition reaction of polymerism.Herein, as polyol component, due to PCDL Lack flexibility, therefore typically can be used (referring for example to patent documents 3) such as polyethers, polyester.

In recent years, require that flexibility, the further of bendability are carried for the carbamate resins containing unsaturated group Height, and the cured film for being obtained by the resin, it is desirable to the durability such as water resistance, heat resistance.

In order to improve the flexibilities of the carbamate resins containing unsaturated group, bendability, it is necessary to the height of resin in itself Molecule quantifies.

But, it is desirable to improve flexibility, bendability of cured film of formation etc. and make the carbamic acid containing unsaturated group During ester resin molecular weight, there is the tendency that the viscosity rising, operability reduction, low temperature fluidity of resin deteriorate.Moreover, by this The cured film that resin is obtained has the tendency of bendability under low temperature, grip reduction, and water resistance, heat resistance are also insufficient.

Prior art literature

Patent document

Patent document 1：Japanese Laid-Open 2007-238797 publications

Patent document 2：Japanese Laid-Open 2009-280665 publications

Patent document 3：Japanese Laid-Open 2003-40965 publications

The content of the invention

Problems to be solved by the invention

The present invention be in view of above such background technology and make, the first problem be there is provided：Take into account to ultraviolet Chemical proofing, the coating urethane resin compositions of durability and soft feel and the sense of touch painting of absorbent etc. Material composition, the second problem be there is provided：Possess sufficient operating characteristics and low temperature fluidity and formed cured film it is low Warm bendability, grip, water resistance, heat resistance also excellent active energy ray-curable resin composition.

The solution used to solve the problem

The present inventor etc. have made intensive studies to solve above-mentioned problem, as a result complete the present invention.

That is, the present invention includes embodiment as shown below.

[1] a kind of coating urethane resin compositions, it is comprising polyalcohol (A), polyisocyanates (B) and disappeared The polyurethane resin composition of photo etching (D), it is characterised in that polyalcohol (A) includes PCDL (a1) and hydroxyl-functional The PEPA (a2) that group's number is more than 3, the average hydroxyl functional group number of polyalcohol (A) be 2.3~3.5, hydroxyl value be 70~ 285mgKOH/g, and the mass ratio of (a1) and (a2) is (a1)/(a2)=75/25~55/45.

[2] the coating urethane resin compositions according to above-mentioned [1], it is characterised in that polyalcohol (A) is wrapped Contain：The PEPA (a2) and hydroxy functional group number that PCDL (a1), hydroxy functional group number are more than 3 are more than 2 And the PEPA (a3) less than 3.

[3] the coating urethane resin compositions according to above-mentioned [1] or [2], it is characterised in that polyester is more First alcohol (a2), (a3) are PEPAs obtained from by making cyclic ester compounds progress ring opening polyaddition.

[4] the coating urethane resin compositions according to any one of above-mentioned [1] to [3], its feature exists In polyisocyanates (B) includes the tripolymer of aliphatic isocyanates.

[5] the coating urethane resin compositions according to any one of above-mentioned [1] to [4], wherein, delustring Agent (D) contains selected from least one of group being made up of inorganic micro powder body and organic micropowder body.

[6] the coating urethane resin compositions according to any one of above-mentioned [1] to above-mentioned [4], it is special Levy and be, delustering agent (D) is silica.

[7] a kind of feel coating, it includes the coating carbamate any one of above-mentioned [1] to above-mentioned [6] Resin combination.

[8] a kind of active energy ray-curable resin composition, it is to include polyalcohol (A), (methyl) acrylate (a6) and polyisocyanates (B) polyurethane resin composition, it is characterised in that polyalcohol (A) be selected from by comprising 3- methyl- 1,5- pentanediols as monomeric unit PCDL (a4) and include the poly- carbon of the construction unit shown in following formula A At least one of group of acid esters glycol (a5) composition, (methyl) acrylate (a6) includes more than 1 hydroxyl and more than 1 (methyl) acryloyl group.

[9] active energy ray-curable resin composition according to above-mentioned [8], it is characterised in that above-mentioned poly- carbon The number-average molecular weight of acid esters glycol (a4) is 300~5000 scope.

[10] active energy ray-curable resin composition according to above-mentioned [8], it is characterised in that above-mentioned poly- carbon Acid esters glycol (a5) includes the construction unit shown in following formula A and the construction unit shown in following Formula Bs.

(in formula, R is separately divalent alkyl, optionally with substituent.The carbon atom of more than 1 in above-mentioned alkyl Optionally by divalent aromatic group, divalent hetero ring type base or divalent crosslinking carbocylic radical replace, in above-mentioned alkyl in addition to end The carbon atom of more than 1 is optionally replaced by oxygen atom or sulphur atom.)

[11] active energy ray-curable resin composition according to above-mentioned [8] or [10], it is characterised in that on It is the compound for including the structure shown in the structure and following general formula Ds shown in following formula C to state PCDL (a5), with n/ The ratio of m=80/20~5/95 (mol ratio) contains the structure shown in following formula C and the structure shown in following general formula Ds.

(in formula, R is separately divalent alkyl, optionally with substituent.The carbon atom of more than 1 in above-mentioned alkyl Optionally by divalent aromatic group, divalent hetero ring type base or divalent crosslinking carbocylic radical replace, in above-mentioned alkyl in addition to end The carbon atom of more than 1 is optionally replaced by oxygen atom or sulphur atom.N >=1, m >=1.)

[12] active energy ray-curable resin composition according to any one of above-mentioned [8], [10] or [11], Characterized in that, the number-average molecular weight of above-mentioned PCDL (a5) is 800~5000 scope.

[13] active energy ray-curable resin composition according to any one of above-mentioned [8] to [12], it is special Levy and be, the molecular weight of above-mentioned (methyl) acrylate (a6) is 100~3000 scope.

[14] active energy ray-curable resin composition according to any one of above-mentioned [8] to [13], it is special Levy and be, above-mentioned (methyl) acrylate (a6) is selected from by acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, third The 6-caprolactone addition product of olefin(e) acid 2- hydroxy methacrylates, Beta-methyl-valerolactone addition product, the metering system of acrylic acid 2- hydroxy methacrylates What the 6-caprolactone addition product of sour 2- hydroxy methacrylates and the Beta-methyl of 2-hydroxyethyl methacrylate-valerolactone addition product were constituted It is at least one kind of in group.

[15] active energy ray-curable resin composition according to any one of above-mentioned [8] to [14], it is special Levy and be, above-mentioned polyisocyanates (B) is in the group being made up of aliphatic diisocyanate and alicyclic diisocyanate It is at least one kind of.

[16] active energy ray-curable resin composition according to any one of above-mentioned [8] to [15], it is special Levy and be, the number-average molecular weight of above-mentioned polyurethane resin composition is 1000~200000 and degree of unsaturation is 0.1~1mol/ kg。

[17] active energy ray-curable resin composition according to any one of above-mentioned [8] to [16], it is special Levy and be, also containing relative to photopolymerization initiation of the above-mentioned mass parts of polyurethane resin composition 100 for 0.01~15 mass parts Agent.

[18] a kind of coating, it is as the active energy ray curable resin any one of above-mentioned [8] to [17] Composition formation.

It should be noted that in the present invention, " (methyl) acryloyl group " refers to acryloyl group or methylacryloyl, " (first Base) acrylate " refer to acrylate or methacrylate.

The effect of invention

For the coating urethane resin compositions of the present invention, as the first effect, it can be formed and take into account resistance toization Learn film of the medicine (particularly UV resistant absorbent) with soft feel (soft feel).In addition, according to this hair It is bright, as the second effect, it can provide：Possesses sufficient operability and low temperature fluidity, curing performance and the formation of resin The low-temperature bending of cured film, grip also excellent active energy ray-curable resin composition.

Embodiment

Hereinafter, the present invention is described in detail.

The 1st aspect of the present invention is related to a kind of coating urethane resin compositions, its be comprising polyalcohol (A), The polyurethane resin composition of polyisocyanates (B) and delustering agent (D), it is characterised in that polyalcohol (A) includes makrolon two Alcohol (a1) and the PEPA (a2) that hydroxy functional group number is more than 3, the average hydroxyl functional group number of polyalcohol (A) is 2.3 ~3.5, hydroxyl value is 70~285mgKOH/g, and the mass ratio of (a1) and (a2) is (a1)/(a2)=75/25~55/45.

In addition, the 2nd aspect of the present invention is related to a kind of active energy ray-curable resin composition, it is comprising many The polyurethane resin composition of first alcohol (A), (methyl) acrylate (a6) and polyisocyanates (B), it is characterised in that polyalcohol (A) be selected from by comprising 3- methyl isophthalic acids, 5- pentanediols as monomeric unit PCDL (a4) and include above-mentioned formula At least one of group of PCDL (a5) composition of construction unit shown in A, (methyl) acrylate (a6) includes 1 Individual above hydroxyl and more than 1 (methyl) acryloyl group.The active energy ray-curable resin composition of the present invention is as be described hereinafter It can also be used like that as coating.

In the 1st aspect of the present invention, polyalcohol (A) refers to, includes PCDL (a1) and PEPA (a2) Polyalcohol or include the polyalcohol of PCDL (a1), PEPA (a2) and (a3).

PCDL (a1) can be sub- by the dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, carbonic acid The luxuriant and rich with fragrance ester of the alkylene carbonate such as ethyl ester, propylene carbonate esters, diphenyl carbonate, carbonic acid dinaphthyl ester, carbonic acid bianthraquinone, carbonic acid two, The reaction of the carbonates such as the diaryl carbonates esters such as the indane ester of carbonic acid two, carbonic acid naphthane ester and glycol and obtain.

In addition, as PCDL (a1), PCDL described later (a4), PCDL can be used (a5)。

As glycol, selected from ethylene glycol, 1,2-PD, 1,3-PD, 1,2- butanediols, 1,3-BDO, Isosorbide-5-Nitrae- Butanediol, 1,5- pentanediols, 1,6-HD, 1,8- ethohexadiols, 1,9- nonanediols, 3- methyl isophthalic acids, 5- pentanediols, 3,3- dihydroxies Methyl heptane, diethylene glycol, DPG, neopentyl glycol, diethylene glycol, DPG, hexamethylene -1,4- glycol, hexamethylene - 1,4- dimethanols, dimeric dibasic acid glycol, the oxirane of bisphenol-A, propylene oxide adduct, double (beta-hydroxy ethyl) benzene, benzene diformazan The low molecular polylol group such as alcohol, glycerine, trimethylolpropane, pentaerythrite.They can be used alone can also combine 2 kinds with On use.

As the PCDL (a1) in the present invention, from the viewpoint of the easiness, chemical proofing obtained, Preferably, using alkylene carbonates as carbonates, using 1,6- hexylene glycols as glycols, to be reacted.

PEPA (a2) in the present invention is the polyfunctional PEPA that hydroxy functional group number is more than 3, special It is not preferably, the PEPA obtained by the polyalcohol comprising polyalcohol and dicarboxylic acid component；By initiator of polyalcohol, The cyclic ester compounds such as lactone are made to carry out polyalcohol obtained from ring opening polyaddition.

As above-mentioned polyalcohol, trimethylolpropane, glycerine, pentaerythrite, sorbierite etc. can be enumerated, can not made Performance reduction in the range of be applied in combination ethylene glycol, diethylene glycol, propane diols, butanediol, neopentyl glycol, hexamethylene glycol, The functional alcohol of DPG, trimethylene etc. 2.These alcohol and oxalic acid, malonic acid, maleic acid, adipic acid, wine can be used It is poly- that the polyacids such as stone acid, pimelic acid, decanedioic acid, phthalic acid, terephthalic acid (TPA) are made by known method of condensing Ester polyol.

In addition, as preferred lactone, can enumerate beta-propiolactone, beta-butyrolactone, gamma-butyrolacton, β-valerolactone, Gamma-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-hexalactone, δ-caprolactone, 6-caprolactone, Alpha-Methyl-ε-oneself Lactone, Beta-methyl -6-caprolactone, 4- methylcaprolactones, γ-decalactone, ε-decalactone, ε-palm lactone etc., will can be selected from One kind or two or more mixing in them and use.Wherein, the stability and economy aspect when polymerization, preferably It is, using trimethylolpropane as the ring opening polyaddition thing of the 6-caprolactone of initiator.

The hydroxy functional group number of PEPA (a3) in the present invention is 2 less than 3, it is therefore particularly preferred that by The PEPA that glycol is obtained with dicarboxylic acid component；By initiator of glycol, opened the cyclic ester compounds such as lactone Polyalcohol obtained from cycloaddition polymerization.

As above-mentioned glycol, ethylene glycol, 1,2-PD, 1,3-PD, 1,2- butanediols, 1,3- fourths two can be enumerated Alcohol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,8- ethohexadiols, 1,9- nonanediols, 3- methyl isophthalic acids, 5- pentanediols, 3,3- dihydroxymethyls heptane, diethylene glycol, DPG, neopentyl glycol, hexamethylene -1,4- glycol, hexamethylene -1,4- diformazans Alcohol, dimeric dibasic acid glycol, the oxirane of bisphenol-A, propylene oxide adduct, double (beta-hydroxy ethyl) benzene, benzene dimethanols etc., can be with Trimethylolpropane, glycerine, pentaerythrite, sorbierite etc. is applied in combination.These alcohol and oxalic acid, malonic acid, horse can be used Carry out the polyacids such as sour, adipic acid, tartaric acid, pimelic acid, decanedioic acid, phthalic acid, terephthalic acid (TPA) and pass through known condensation Method and the PEPA made.

In addition, as preferred lactone, can enumerate beta-propiolactone, beta-butyrolactone, gamma-butyrolacton, β-valerolactone, Gamma-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-hexalactone, δ-caprolactone, 6-caprolactone, Alpha-Methyl-ε-oneself Lactone, Beta-methyl -6-caprolactone, 4- methylcaprolactones, γ-decalactone, ε-decalactone, ε-palm lactone etc., will can be selected from One kind or two or more mixing in them and use.Wherein, the stability and economy aspect when polymerization, preferably It is, using ethylene glycol as the ring opening polyaddition thing of the 6-caprolactone of initiator.

PCDL (a1) and PEPA (a2) or ((a2)+(a3)) mass ratio for (a1)/(a2)= 75/25~55/45, the scope of (a1)/((a2)+(a3))=75/25~55/45, more preferably (a1)/(a2)=70/30~ 60/40th, the scope of (a1)/((a2)+(a3))=70/30~60/40.By making (a1)/(a2) or (a1)/((a2)+(a3)) Mass ratio be the scope, have aggregation force and carbamate groups concentration, polyester polyol content using PCDL Harmony and assign the tendency that soft sense of touch, chemical proofing are improved.

The PCDL (a1) can merely be mixed and used with PEPA (a2), (a3), using passing through The polyalcohol that ester exchange reaction is obtained, so that chemical proofing and soft feel are taken into account, and to the dissolubility of solvent Improve.

The average hydroxyl functional group number of polyalcohol (A) is 2.3~3.5, more preferably 2.5~3.0 scope.It is average by making Hydroxy functional group number is 2.3~3.5, has and assigns soft sense of touch using cross-linked structure, the harmony of polyester polyol content, The tendency that chemical proofing is improved.

The average hydroxyl value of polyalcohol (A) is 75~285mgKOH/g, more preferably 90~180mgKOH/g.By making average hydroxyl It is worth for 75~285mgKOH/g, has and assigned using the aggregation force of PCDL and the harmony of carbamate groups concentration The tendency that the sense of touch of softness, chemical proofing are improved.

In the present invention, in order to embody soft feel, as delustering agent (D), using selected from by the inorganic of 1~30 μm of particle diameter At least one of group of powder body and organic micropowder body composition.As inorganic micro powder body, silica is preferably used, can also Use the bases such as glass, mica, zeolite, diatomite, graphite, clay, talcum, calcium carbonate, metal, metal oxide etc..As Organic micropowder body, preferably uses polyurethane pearl, can also use the various resins such as acrylic resin, polyamide, silicon rubber, paper Slurry, cellulose etc..Two or more can also be applied in combination in these powder bodies.Powder body is preferably spherical, and it is 1 to preferably use particle diameter ~30 μm of powder body, more than at that time, as coarse sense of touch.Compounding amount for polyurethane resin composition 1~30 mass %, Preferably 10~20 mass %.

In the present invention, organic solvent can be used as needed.

As organic solvent, can suitably select in presence of organic solvent not impact reaction is organic molten Agent.As the concrete example of organic solvent, the clicyclic hydrocarbons such as the aliphatic hydrocarbons such as octane, hexamethylene, hexahydrotoluene can be enumerated The esters such as the ketones such as class, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol Ether acetate, propylene glycol methyl ether acetate, 3- methyl -3- methoxybutyls acetic acid esters, ethyl -3- ethoxy-c acid esters etc. The halogenated hydrocarbons such as the ethers such as diol alcohol esters, dioxane, iodomethane, monochlorobenzene, 1-METHYLPYRROLIDONE, dimethyl methyl Acid amides, dimethyl acetamide, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide polar aprotic solvent etc..These solvents can be independent Using or combine two or more and use.

As the concrete example of the polyisocyanates (B) reacted with polyalcohol (A), can enumerate aromatic diisocyanate, Aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, using these polyisocyanates as raw material Obtained from the polyisocyanates containing isocyanurate group, the polyisocyanates containing uretdion, containing uretdion and isocyanide urea The polyisocyanates of perester radical, the polyisocyanates of amido-containing acid ester base, the polyisocyanates of special allophanates containing base, containing contracting The polyisocyanates of two urea groups, polyisocyanates of the base containing uretonimine etc., can be used alone or in combination of two or more kinds.

Urethane reaction can also be reacted under without catalyst, but anti-using known urethane Catalyst is answered to promote reaction.The concrete example for the catalyst that can be used in being reacted as urethane, Ke Yiju Go out the organo-metallic compounds such as dibutyltin diacetate, dibutyl tin laurate, tin dilaurate dioctyl tin, triethylene two The organic amines such as amine, triethylamine or its salt.

In the present invention, in order to further improve physical property and add various physical property, it can use general as additive , surfactant, levelling agent, viscosity modifier, antigelling agent, fire retardant, plasticizer, antioxidant, ultra-violet absorber, Hydrolysis inhibitor, antiseptic, filler, internal mold release, strengthening material, conductivity-imparting agent, charge control agent, antistatic additive, The processing aids such as dispersant, lubricant, dyestuff, pigment.

The coating urethane resin compositions of the present invention can be used for an electrical article, OA as soft feel coating Product, mobile phone, interior automotive trim parts, leather surface processing etc., can take into account the sense of touch of softness and to cosmetics etc. In contained ultra-violet absorber, the durability of insecticide.

Herein, the ultraviolet to being used in the index for the evaluation of UV resistant absorbent enumerated in the effect of the present invention Absorbent is illustrated.As ultra-violet absorber, contained p-aminobenzoic acid system, cinnamic acid predominantly in cosmetics etc. System, benzophenone series, salicylic acid system, benzoyl triazole system, other fragrant family ultra-violet absorbers and by them more than one The mixture of formation, these materials are moved to the polyurethane resin composition of formed body, coating material, so that visible formed body table The appearance degradation in face, with adhesive phenomenon.

In these ultra-violet absorbers, particularly ESCALOL 567, BMDBM, water Poplar acid 3,3,5- 3-methyl cyclohexanols ester, 4- tert-butyl-benzoyls (4- methoxybenzoyls base) methane, 3,3- diphenyl -2- cyanogen Base 2-EHA is likely to become formed body, the big Obstacle Factors of the UV resistant absorbent of coating material.

As insecticide, mostly using DEET (DEET), it is known that it has excellent keep away The effect of mosquito, but skin or damage synthetic leather, plastics can be infiltrated into.

Then, second embodiment of the present invention is illustrated.

In second embodiment of the present invention, PCDL (a4) refers to, with active by carbonic acid ester bond connection From the macromolecular chain of the alkyl of polyalcohol and the hydroxyl being connected with two ends of the macromolecular chain, and with shown in following formula Construction unit.

The PCDL (a4) used in second embodiment of the present invention can be by dimethyl carbonate, carbonic acid two The alkylene carbonate such as the dialkyl carbonates such as ethyl ester, ethylene carbonate, propylene carbonate esters, diphenyl carbonate, carbonic acid two The carbonic esters such as the diaryl carbonates esters such as the luxuriant and rich with fragrance ester of naphthalene ester, carbonic acid bianthraquinone, carbonic acid two, the indane ester of carbonic acid two, carbonic acid naphthane ester Class and 3- methyl isophthalic acids, the dealcoholization of 5- pentanediols or de- phenol reactant and obtain.

In second embodiment of the present invention, in PCDL (a4), can also by 3- methyl isophthalic acids, 5- pentanediols with Except 3- methyl isophthalic acids, the diol combination outside 5- pentanediols is used.

As except 3- methyl isophthalic acids, the glycol outside 5- pentanediols is not particularly limited, for example, can enumerate ethylene glycol, 1, 2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1, 8- ethohexadiols, 1,9- nonanediols, 3,3- dihydroxymethyls heptane, diethylene glycol, DPG, neopentyl glycol, hexamethylene -1,4- two Alcohol, hexamethylene -1,4- dimethanols, dimeric dibasic acid glycol, the oxirane of bisphenol-A or propylene oxide adduct, double (beta-hydroxy second Base) low molecular polylol such as benzene, benzene dimethanol, glycerine, trimethylolpropane, pentaerythrite.

As the manufacture raw material, 3- methyl isophthalic acids of PCDL (a4), 5- pentanediols and glycol in addition Mol ratio ([3- methyl isophthalic acids, 5- pentanediols]：[glycol in addition]) preferably 100：0~1：99,3- methyl isophthalic acids, 5- pentanediols During less than 1 mole of %, there is the worry that fluidity deteriorates.

In second embodiment of the present invention, it is considered to when the easiness of synthesis, handling easiness, PCDL (a4) Number-average molecular weight preferably 300~5000 scope.

In addition, in second embodiment of the present invention, PCDL (a5) refers to, with being connected by carbonic acid ester bond The hydroxyl for having the macromolecular chain of the alkyl from polyalcohol and being bonded in two ends of the macromolecular chain, such as with above-mentioned Copolymerization (including block random etc.) structure of construction unit shown in formula A and the construction unit shown in above-mentioned Formula B.

As the compound with the construction unit shown in above-mentioned formula A, for example, it can enumerate and be opened 6-caprolactone Polycaprolactone polyol obtained from cyclopolymerization.

Compound with the construction unit shown in above-mentioned Formula B can pass through the carbon such as dimethyl carbonate, diethyl carbonate The alkylene carbonate such as acid dialkyl esters, ethylene carbonate, propylene carbonate esters, diphenyl carbonate, carbonic acid dinaphthyl ester, carbonic acid Carbonates and the second two such as the diaryl carbonates esters such as the luxuriant and rich with fragrance ester of bianthraquinone, carbonic acid two, the indane ester of carbonic acid two, carbonic acid naphthane ester Alcohol, 1,2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6- oneself two Alcohol, 1,8- ethohexadiols, 1,9- nonanediols, 3- methyl isophthalic acids, 5- pentanediols, 3,3- dihydroxymethyls heptane, diethylene glycol, dipropyl two Alcohol, neopentyl glycol, hexamethylene -1,4- glycol, hexamethylene -1,4- dimethanols, dimeric dibasic acid glycol, the oxirane of bisphenol-A, epoxy The low molecular polylol such as propane addition product, double (beta-hydroxy ethyl) benzene, benzene dimethanol, glycerine, trimethylolpropane, pentaerythrites The reaction of class and obtain.Wherein it is possible to be adapted to using the polycarbonate polyol obtained by 1,6- hexylene glycols and diethyl carbonate.

In above-mentioned Formula B, as R, as long as being just not particularly limited for divalent alkyl, for example, methylene, sub- second can be enumerated Base, propylidene, isopropylidene, butylidene, isobutylene, tertiary butylidene, pentylidene, isopentylidene, hexylidene, isohexylidene, The aliphatic alkyls such as heptamethylene, different heptamethylene, octamethylene, different octamethylene, ring butylidene, ring pentylidene, cyclohexylene, ring sub- heptan Aromatic hydrocarbyls such as the alicyclic alkyls such as base, phenylene, toluylene, biphenylene, naphthylene etc..

In above-mentioned Formula B, R optionally has substituent.As substituent, hydroxyl, carboxyl, amino etc. can be enumerated.

In above-mentioned R, the carbon atom of more than 1 in alkyl can be by divalent aromatic group, divalent hetero ring type base or divalent Crosslinking carbocylic radical is replaced.For example, can enumerate in above-mentioned R, carbon atom more than 1 in divalent alkyl is by with benzene, first Material that the compound of the aromatic rings such as benzene, naphthalene is replaced, by the compound institute with heterocycles such as morpholine, imidazoles, pyridine, quinoline Substituted material, the material that the compound of carbocyclic ring is replaced is crosslinked with norbornane, naphthalane etc., R institutes in formula can be enumerated The carbon atom of more than 1 outside the end of the alkyl shown has ether structure, peroxide structure by what oxygen atom was replaced Material or the material with sulfide based structural, disulfide structure replaced by sulphur atom.

PCDL (a5) contains the construction unit shown in above-mentioned formula A and the construction unit shown in above-mentioned Formula B When, mole of the construction unit and the construction unit shown in above-mentioned Formula B shown in above-mentioned formula A in PCDL (a5) Than preferably 80：20~5：95th, further preferred 15：85~40：60.That is, PCDL (a5) is includes above-mentioned formula C institutes The compound for the structure shown in structure and above-mentioned general formula D shown, and preferably with the ratio of n/m=80/20~5/95 (mol ratio) Containing the structure shown in the structure shown in above-mentioned formula C and above-mentioned general formula D, further preferably with 15：85~40：60 (mol ratios) Ratio contain structure shown in above-mentioned formula C and the structure shown in above-mentioned general formula D.When outside scope, there is what fluidity deteriorated Worry.

In addition, above-mentioned PCDL (a5) contains the structure shown in above-mentioned formula C and the structure shown in above-mentioned general formula D When, preferably contained with the ratio of n/m=80/20~5/95 (mol ratio) shown in structure and above-mentioned general formula D shown in above-mentioned formula C Structure.

In second embodiment of the present invention, it is considered to when the easiness of synthesis, handling easiness, PCDL (a5) Number-average molecular weight preferably 800~5000, further preferred 1000~3500.

In second embodiment of the present invention, as comprising more than 1 hydroxyl and more than 1 (methyl) acryloyl group (methyl) acrylate (a6), is not particularly limited, be molecular weight for 100~3000, be preferably 100~2000, it is further excellent Elect the material of 100~1000 scope as, for example, can enumerate acrylic acid 2- hydroxy methacrylates, hydroxypropyl acrylate, poly- second two Alcohol mono acrylic ester, polypropylene glycol mono acrylic ester, the 6-caprolactone addition product of acrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxyls Esters of acrylic acid, the metering systems such as the Beta-methyl of ethyl ester-valerolactone addition product, glycerol mono-acrylate, glycerol diacrylate Sour 2- hydroxy methacrylates, hydroxy propyl methacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, first The 6-caprolactone addition product of base acrylic acid 2- hydroxy methacrylates, Beta-methyl-valerolactone addition product of 2-hydroxyethyl methacrylate, The methyl acrylic esters such as glycerin monomethyl acrylic ester, glycerine dimethacrylate, allyl alcohol, glycerine monoallyl Allyl compound class such as ether, glycerol diallyl ether etc..

Wherein, preferably acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy methacrylates ε-oneself Lactone addition product, Beta-methyl-valerolactone addition product of acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate ε-oneself in Beta-methyl-valerolactone addition product of ester addition product, 2-hydroxyethyl methacrylate, particularly preferred acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate.In addition, as (a6) composition, can be used alone above-mentioned a kind of compound, can also combine makes Use two or more.

In second embodiment of the present invention, as polyisocyanates (B), it can use described in first embodiment Polyisocyanates (B).Wherein, preferred aliphat isocyanates, ester ring type diisocyanate, further preferred isophorone two are different Cyanate.

In second embodiment of the present invention, above-mentioned polyurethane resin composition can be formed as polyalcohol (A), (first Base) acrylate (a6) and polyisocyanates (B) carbamate resins reaction product, containing unsaturated group.

In second embodiment of the present invention, the number-average molecular weight of above-mentioned polyurethane resin composition is preferably 1000~ 200000.When number-average molecular weight is less than above range, there are the flexibility of the cured film formed by the resin, elongation to become not fill The tendency divided, during more than above range, crystallinity, viscosity become very high, therefore, and have manufacture stability ensures that becoming difficult inclines To.Preferred number-average molecular weight is 10000~50000.

In addition, in second embodiment of the present invention, the degree of unsaturation of above-mentioned polyurethane resin composition is preferably 0.1~ 1mol/kg.Herein, degree of unsaturation refers to, the molal quantity of (a6) composition required when manufacturing resin 1kg is set into α mol, will (a6) when the number of free-radical polymerised unsaturated bond contained in the molecule of composition 1 is set to β, obtained value is calculated with α × β.No When saturation degree is less than above range, the crosslink density for the cured film for having curing performance insufficient or being formed by the resin diminishes And the tendency of sufficient surface cure can not be obtained, during more than above range, although sufficient surface cure can be obtained, But cured film is hardened, have the tendency of to lack flexibility, elongation.Preferred scope is 0.1~0.5mol/kg.

In second embodiment of the present invention, above-mentioned polyurethane resin composition will can for example be selected from by above-mentioned (a4) and (a5) at least one of group composition of composition is put into organic solvent with (a6) composition and (B) composition, make its reaction so as to Manufacture.

Herein, reaction temperature is usually 20~200 DEG C, preferably 30~150 DEG C of scope.As long as in addition, can suitably enter Row reaction is until isocyanate residue disappears, and the reaction time is usually 10 minutes~48 hours., can be with as organic solvent Using the organic solvent described in first embodiment, these solvents can be used alone or in combination of two or more kinds.

During the reaction, the catalysts for the reaction for promoting hydroxyl and NCO can be added as needed.As Such catalysts, can enumerate plumbi oleas, tetrabutyltin, trichloride antimony, triphenyl aluminum, trioctylaluminum, zinc naphthenate, Zirconium naphthenate, dibutyl tin laurate, tin dilaurate dioctyl tin, tetra-n-butyl -1,3- diacetoxies distannoxane, 1, 4- diazas [2.2.2] double-octane, N-ethylmorpholine etc..

In addition, selected from by least one of above-mentioned (a4) and (a5) group constituted composition and (a6) composition and (B) composition As long as degree of unsaturation, number-average molecular weight of the ratio according to required by above-mentioned polyurethane resin composition etc. and determine just do not have It is particularly limited to.For example, in order to manufacture, number-average molecular weight is 1000~200000 and degree of unsaturation is the above-mentioned of 0.1~1mol/kg Polyurethane resin composition, will be selected from by least one of above-mentioned (a4) and (a5) group constitute composition and (a6) composition and (B) when the total amount (solid constituent) of composition is set to 100 mass %, it is preferred that selected from the group being made up of above-mentioned (a4) and (a5) At least one of composition be that 50~90 mass %, (a6) composition are that 2~20 mass %, (B) composition are 5~40 mass %.Separately Outside, in the case of using catalysts, relative to selected from by least one of above-mentioned (a4) and (a5) group constituted composition With the mass parts of total amount (solid constituent) 100 of (a6) composition and (B) composition, preferably made with the scope of 0.005~1.0 mass parts With.

The active energy ray-curable resin composition of second embodiment of the present invention is relative to above-mentioned polyurethane tree The mass parts of oil/fat composition 100, the Photoepolymerizationinitiater initiater for preferably comprising 0.01~15 mass parts, can be penetrated by irradiating active-energy Line and obtain solidfied material.

As Photoepolymerizationinitiater initiater, it is not particularly limited, for example, can enumerates acetophenone, methoxyacetophenone, 2,2- bis- Acetophenone, to dimethylamino benzoylformaldoxime, 2,2- dimethoxy -2- phenyl acetophenones, Alpha-hydroxy-α, α '-dimethyl Acetophenone, 2- hydroxyl -2- cyclohexyl benzenes ethyl ketone, 2- methyl isophthalic acids-[4- (methyl thio) phenyl] grade benzene second of -2- morpholinopropanones -1 Benzoin ethers, benzophenone, the 2- chlorine such as ketone, benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl butyl ether Benzophenone, p, p '-dichloro benzophenone, N, N '-tetramethyl -4,4 '-diaminobenzophenone, 4- (2- hydroxyl-oxethyls) benzene The thioxanthene ketone class such as ketone, thioxanthones, CTX, the 2- methyl thioxanthones such as base (2- hydroxyl -2- propyl group) ketone, the oxidation of double acyl groups The ketones such as the ketal such as the phosphine oxides such as phosphine, benzoylphosphine oxide, benzil dimethyl ketal class, camphane -2,3- diketone, phenanthrenequione Deng.These Photoepolymerizationinitiater initiaters can be used alone or in combination of two or more kinds.

It is used as the active energy for solidifying the active energy ray-curable resin composition of second embodiment of the present invention Ray is measured, is not particularly limited, for example, can enumerate electric wire, ultraviolet, luminous ray, laser beam (near infrared ray, visible ray Laser, ultraviolet laser etc.).Its exposure can be adjusted as needed.

It should be noted that the active energy ray-curable resin composition of second embodiment of the present invention is except above-mentioned (a4), outside (a5), (a6), (B) composition, organic solvent, coloring pigment, extender pigment, coating can be compounded as needed and is used Additive etc..

As organic solvent, the organic solvent described in first embodiment can be used, these solvents can individually make With or combine two or more and use.

As coloring pigment, it is not particularly limited, for example, can enumerates titanium oxide, zinc oxide, carbon black, iron oxide (India It is red), chrome yellow, yellow iron oxide, ochre, ultramarine, inorganic series pigments, azo system, naphthols system, pyrazolone system, the anthraquinone such as cobalt green Organic face such as Xi, perylenes system, quinacridone, bisazo system, isoindolinone system, benzimidazole system, phthalocyanine system, quinophthalone system Material.

As extender pigment, it is not particularly limited, for example, can enumerates powdered whiting, clay, kaolin, talcum, heavy Drop property barium sulfate, barium carbonate, white carbon, diatomite etc..

As additive for coatings, it is not particularly limited, for example, can enumerates plasticizer, catalyst, mould inhibitor, froth breaking Agent, levelling agent, pigment dispersing agent, sagging inhibitor, anti-sagging agent, thickener, delustering agent, light stabilizer, ultra-violet absorber etc..

The active energy ray-curable resin composition of the present invention can be suitable for ink, coating, bonding agent, coating The various coating applications such as agent, surface conditioning agent.The rubbing method of the resin combination is not particularly limited, can be from known gimmick In suitably select.In addition, the thickness of coating weight, film, active energy beam exposure etc. can be according to the materials in the face that is coated Deng and be set to appropriate condition.

Film using the active energy ray-curable resin composition formation of the present invention is suitable for for formation The low-temperature bending of cured film, grip, water resistance, the various uses required by heat resistance.

Embodiment

Hereinafter, embodiments of the invention are illustrated, but being not limited to the examples property of the present invention is explained.

[first embodiment]

(manufacture 1 of polyalcohol)

In the reaction unit for being assembled with mixer, thermometer, heater, destilling tower, using 1, the 6- as glycol oneself Glycol (following brief note makees 1,6-HG) is turned into relative to the compounding ratio of diethyl carbonate (following brief note makees DEC) with molar ratio computing 1.08 mode, input 1,6-HG 830g, DEC 771g, and further put into the tetrabutyl titanate as catalysts Ester (following brief note makees TBT) 0.05g, slowly makes temperature rise to 190 DEG C under stream of nitrogen gas.It is slowed by distillating for ethanol And the tower top temperature of destilling tower is at the time of be changed into less than 50 DEG C, reaction temperature keep 190 DEG C unchangeably slowly carry out depressurizing it is straight To 1.3kPa, it is further set to react 7 hours with 1.3kPa pressure.Further with 190 DEG C of reaction temperature 1.3kPa with Under decompression under, it is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 (mg-KOH/g), obtain PCDL (Polyol-1).Gained Polyol-1 hydroxyl value is 55.6 (mg-KOH/g).

(manufacture 2 of polyalcohol)

Polyol-1 645g, polycaprolactonetriol (PCL-305) 350g, the 1,6- obtained in the manufacture 1 for putting into polyalcohol HG 4.85g, carry out ester exchange reaction 5 hours with 190 DEG C, obtain polyalcohol (Polyol-2).Gained Polyol-2 hydroxyl value is 150.8(mg-KOH/g)。

(manufacture 3 of polyalcohol)

Polyol-1 687g, polycaprolactonetriol (PCL-305) 300g, the 1,6- obtained in the manufacture 1 for putting into polyalcohol HG 13.1g, carry out ester exchange reaction 5 hours with 190 DEG C, obtain polyalcohol (Polyol-3).Gained Polyol-3 hydroxyl value is 143.2(mg-KOH/g)。

(manufacture 4 of polyalcohol)

Polyol-1 503g, polycaprolactone glycol (PCL-220) 215g obtained in the manufacture 1 for putting into polyalcohol, with 190 DEG C carry out ester exchange reaction 5 hours, obtain polyalcohol (Polyol-4).Gained Polyol-4 hydroxyl value is 56.6 (mg- KOH/g)。

(manufacture 5 of polyalcohol)

In the reaction unit for being assembled with mixer, thermometer, heater, destilling tower, to be used as the 1,6-HG of glycol Relative to diethyl carbonate (following brief note make DEC) compounding ratio in the way of molar ratio computing turns into 1.16, put into 1,6-HG 841g, DEC 723g, and further put into tetrabutyl titanate ester (following brief note make TBT) 0.05g as catalysts, Temperature is slowly set to rise to 190 DEG C under stream of nitrogen gas.It is slowed by and the tower top temperature of destilling tower is changed into distillating for ethanol At the time of less than 50 DEG C, reaction temperature is kept for 190 DEG C unchangeably slowly carry out decompression up to 1.3kPa, with 1.3kPa pressure It is further set to react 7 hours.Further with 190 DEG C of reaction temperature under below 1.3kPa decompression, persistently reacted Until the hydroxyl value of reactant reaches 110~114 (mg-KOH/g), PCDL (Polyol-5) is obtained.Gained Polyol- 5 hydroxyl value is 112.4 (mg-KOH/g).

(manufacture 6 of polyalcohol)

Polyol-1 854g, polycaprolactonetriol (PCL-305) 100g, the 1,6- obtained in the manufacture 1 for putting into polyalcohol HG 46.2g, carry out ester exchange reaction 5 hours with 190 DEG C, obtain polyalcohol (Polyol-6).Gained Polyol-6 hydroxyl value is 122.4(mg-KOH/g)。

(manufacture 7 of polyalcohol)

In the reaction unit for being assembled with mixer, thermometer, heater, destilling tower, to be used as the 1,6-HG of glycol Compounding ratio relative to DEC is in the way of molar ratio computing turns into 1.05, input 1,6-HG 826g, DEC 787g, and enters one Step input slowly makes temperature as tetrabutyl titanate ester (following brief note makees TBT) 0.05g of catalysts under stream of nitrogen gas Degree rises to 190 DEG C.It is slowed by and at the time of the tower top temperature of destilling tower is changed into below 50 DEG C in distillating for ethanol, reaction temperature Kept for 190 DEG C unchangeably slowly carry out decompression until 1.3kPa, further makes it react 7 hours with 1.3kPa pressure.Enter One step is with 190 DEG C of reaction temperature under below 1.3kPa decompression, and lasting progress reaction is until the hydroxyl value of reactant is changed into 35 ~39 (mg-KOH/g), obtain polyalcohol.The hydroxyl value of gained polyalcohol is 37.6 (mg-KOH/g).Then the gained is put into polynary Alcohol 575g, polycaprolactonetriol (PCL-305) 400g, polycaprolactone glycol (PCL-210) 25g, carry out ester exchange anti-with 190 DEG C Answer 5 hours, obtain PCDL (Polyol-7).Gained Polyol-7 hydroxyl value is 145.3 (mg-KOH/g).

(making of evaluation film)

As shown in the embodiment 1 of table 1, by polyalcohol 20g, delustering agent ACEMATT OK900 (EVONIK company systems two 7.5 μm of silica, particle diameter) 5g, levelling agent BYK-331 (BYK Japan KK. systems) 0.25g, catalyst DOTDL (Kishida Chemical Ltd., Co.) 0.05g compoundings, it is also contemplated that during curing agent, further add in the way of as solid constituent=30% Plus butyl acetate 81.3g, then mixed, obtain host.Then, with host hydroxyl moles and curing agent NCO Molal quantity turns into 1/1 mode, and curing agent C-HXLV9.5g is mixed with host, is coated on base material (ABS resin) and causes drying Thickness turns into 60 μm, with 80 DEG C of progress drying in 2 hours, is further cured 96 hours with 25 DEG C, thus makes film.Use the painting Film carries out the evaluation of physical property.

For embodiment 2~5, comparative example 1~6, film is also made similarly to Example 1, carries out the evaluation of physical property.

In addition, the raw material used in the present invention is shown in following.

PCL-305 polycaprolactonetriols (molecular weight=550, hydroxyl value=305, functional group number=3) Daicel Corporation systems

PCL-312 polycaprolactonetriols (molecular weight=1250, hydroxyl value=135, functional group number=3) Daicel Corporation systems

PCL-220 polycaprolactone glycols (molecular weight=2000, hydroxyl value=56.1, functional group number=2) Daicel Corporation systems

PCL-210 polycaprolactone glycols (molecular weight=1000, hydroxyl value=112, functional group number=2) Daicel Corporation systems

C-HXLV polyisocyanate curing agents (NCO content=23.2%) TOSOH Co., Ltd system

For gained film, evaluated for following items, result described in table 1.

1. sense of touch

For the surface of film, using abrasive feel testing machine KSE-SE (Keto tech Co., Ltd.s system), with piano wire Friction member, load 25g, determine the frictional force standard as the frictional force (μ) of the index of clamping sense and the index as harsh feeling Deviation (μM D).Will meet 0.5≤μ≤1.0, μM D≤0.012 situation be denoted as "○", be unsatisfactory for 0.5≤μ≤1.0, μM D≤ 0.012 situation is denoted as "×".

2-1. chemical proofing

<UV resistant absorbent>

The solution of glycerine 3% of following compounds is modulated respectively, each modulating liquid 1 is added dropwise on film and drips, and it is small to place 1 with 40 DEG C Shi Hou, is wiped, with visual valuation outward appearance.

<Compound>

(1) ESCALOL 567

(2) salicylic acid -2- ethylhexyls

(3) salicylic acid -3,3,5- 3-methyl cyclohexanols ester

(4) 4- tert-butyl-benzoyls (4- methoxybenzoyls base) methane

(5) 3,3- diphenyl -2- alpha-cyanoacrylates -2- ethylhexyls

<Metewand>

Generated in the major part of film be swelled, fold, dissolving (evaluate：×)

Fold (evaluation is generated in the major part of film：△)

Protuberance (evaluation is generated slightly so that the degree of vestige residual is added dropwise on film：○)

Change (evaluation is had no on film：◎)

<Resistance to insecticide>

The DEET solution of ethanol 10% is modulated, modulating liquid 1 is added dropwise on film and drips, after being placed 1 hour with 40 DEG C, is wiped, With visual valuation outward appearance.

<Metewand>

Generated in the major part of film be swelled, fold, dissolving (evaluate：×)

Fold (evaluation is generated in the major part of film：△)

Protuberance (evaluation is generated slightly so that the degree of vestige residual is added dropwise on film：○)

Change (evaluation is had no on film：◎)

[table 1]

[second embodiment]

Production Example 1.

(manufacture 1 of PCDL)

In the reaction unit for being assembled with mixer, thermometer, heater, destilling tower, using as the 3- methyl of glycol- 1,5- pentanediols (following brief note makees MPD) are set to MPD/1,6- with 1,6-HD (following brief note makees 1,6-HG) with molar ratio computing HG=3/7 so that the glycol is turned into relative to the compounding ratio of diethyl carbonate (following brief note makees DEC) with molar ratio computing 1.05, input MPD 248g, 1,6-HG 579g, DEC 787g, and further put into the tetrabutyl titanium as catalysts Acid esters (following brief note makees TBT) 0.05g, slowly makes temperature rise to 190 DEG C under stream of nitrogen gas.Slow down in distillating for ethanol At the time of the tower top temperature of slow and destilling tower is changed into less than 50 DEG C, reaction temperature is kept for 190 DEG C and unchangeably slowly depressurized Until 1.3kPa, further makes it react 7 hours with 1.3kPa pressure.Further with 190 DEG C of reaction temperature in 1.3kPa It is lasting to carry out reaction up to the hydroxyl value of reactant is changed into 35~40 (mg-KOH/g) under following decompression, obtain makrolon two Alcohol (Polyol-8).The hydroxyl value of gained polyol compound is 37.4mg-KOH/g (number-average molecular weight (following Mn)=3000).

Production Example 2.

(manufacture 2 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=3/7 are set to molar ratio computing, with relative to DEC Compounding ratio in the way of molar ratio computing turns into 1.08, input MPD 300g, 1,6-HG 700g, DEC 926.1g, except this it Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 56.1mg-KOH/g (Mn=2000) (Polyol-9)。

Production Example 3.

(manufacture 3 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=3/7 are set to molar ratio computing, with relative to DEC Compounding ratio in the way of molar ratio computing turns into 1.16, input MPD 300g, 1,6-HG 700g, DEC 862.2g, except this it Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 112.2mg-KOH/g (Mn=1000) (Polyol-10)。

Production Example 4.

(manufacture 4 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=5/5 are set to molar ratio computing, with relative to DEC Compounding ratio in the way of molar ratio computing turns into 1.08, input MPD 500g, 1,6-HG 500g, DEC 926.1g, except this it Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 56.1mg-KOH/g (Mn=2000) (Polyol-11)。

Production Example 5.

(manufacture 5 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=9/1 are set to molar ratio computing, with relative to DEC Compounding ratio in the way of molar ratio computing turns into 1.05, input MPD 744g, 1,6-HG 82.7g, DEC 787g, except this it Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 37.4mg-KOH/g (Mn=3000) (Polyol-12)。

Production Example 6.

(manufacture 6 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=9/1 are set to molar ratio computing, with relative to DEC Compounding ratio in the way of molar ratio computing turns into 1.08, input MPD 900g, 1,6-HG 100g, DEC 926.1g, except this it Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 56.1mg-KOH/g (Mn=2000) (Polyol-13)。

Production Example 7.

(manufacture 7 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=9/1 are set to molar ratio computing, with relative to DEC Compounding ratio in the way of molar ratio computing turns into 1.38, input MPD 900g, 1,6-HG 100g, DEC 725.0g, except this it Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 224.0mg-KOH/g (Mn=500) (Polyol-14)。

Production Example 8.

(manufacture 8 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=10/0 are set to molar ratio computing, with relative to DEC compounding ratio is in the way of molar ratio computing turns into 1.08, input MPD 1000g, 1,6-HG 0g, DEC 926.1g, except this Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 56.1mg-KOH/g (Mn=2000) (Polyol-15)。

Production Example 9.

(manufacture 9 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=0/10 are set to molar ratio computing, with relative to DEC compounding ratio is in the way of molar ratio computing turns into 1.05, input MPD 0g, 1,6-HG 827g, DEC 787g, except this it Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 37.4mg-KOH/g (Mn=3000) (Polyol-16)。

Production Example 10.

(manufacture 10 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=0/10 are set to molar ratio computing, with relative to DEC compounding ratio is in the way of molar ratio computing turns into 1.08, input MPD 0g, 1,6-HG 1000g, DEC 926.1g, except this Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 56.1mg-KOH/g (Mn=2000) (Polyol-17)。

Production Example 11.

(manufacture 11 of PCDL)

In the manufacture method same with Production Example 1, MPD/1,6-HG=0/10 are set to molar ratio computing, with relative to DEC compounding ratio is in the way of molar ratio computing turns into 1.16, input MPD 0g, 1,6-HG 1000g, DEC 862.2g, except this Outside, synthesized using same method, so as to obtain the PCDL that hydroxyl value is 112.2mg-KOH/g (Mn=1000) (Polyol-18)。

Production Example 12.

(manufacture 12 of PCDL)

In the manufacture method same with Production Example 1,1,5-PD/1,6-HG=5/5 is set to molar ratio computing, with phase For DEC compounding ratio in the way of molar ratio computing turns into 1.07, input 1,5-PD 385g, 1,6-HG 436g, DEC 814g, in addition, is synthesized using same method, so as to obtain the poly- carbonic acid that hydroxyl value is 56.1mg-KOH/g (Mn=2000) Esterdiol (Polyol-19).

It should be noted that in following comparative example, as Polyol-20, using the Nipporan- of TOSOH Co., Ltd 4010 (poly- Isosorbide-5-Nitrae-butylene adipate, hydroxyl value 56.1mg-KOH/g (Mn=2000)).In addition, as Polyol-21, using PTG-2000SN (polytetramethylene glycol, hydroxyl value 56.1mg-KOH/g (Mn=of Baotugu Chemical Industrial Co., Ltd 2000))。

Embodiment 6.

(manufactures of the carbamate resins containing unsaturated group)

Polyol-8 443.4g, different Buddhist are put into the 2L four-hole boiling flasks for being assembled with mixer, thermometer, heater Your ketone diisocyanate (is abbreviated makees IPDI below) 43.7g, tin dilaurate dioctyl tin (following brief note makees DOTDL) 0.2g and first Ethyl ketone (following brief note makees MEK) 500g, stir about reacts it in 12 hours at 70 DEG C.Afterwards, methacrylic acid 2- hydroxyls are put into Base ethyl ester (following brief note makees HEMA) 12.7g, stir about reacts it in 12 hours at 70 DEG C.

Reaction terminates to confirm not observing isocyanate residue by infrared absorption spectrum.In this way, obtaining containing conduct 50 mass % of solid constituent number-average molecular weight 30000, the degree of unsaturation 0.20mol/kg amino first containing unsaturated group The resin solution of acid ester resin.For gained resin solution, by following methods, operability and low temperature fluidity are evaluated.By result It is shown in table 2, table 3.

(being made using the film of active energy ray-curable resin composition)

Relative to the mass parts of carbamate resins solid constituent 100 containing unsaturated group in gained resin solution, Add Photoepolymerizationinitiater initiater (Ciba Sepcial chemicals Ltd. IRGACURE 184, the 1- hydroxyls of 1.5 mass parts Cyclohexyl-phenyl ketone), resin composition modulation, it is (right that the resin combination is coated on processing release paper with about 200 μm of thickness Evaluated in grip, use PET base material).Afterwards, place 24 hours, make after organic solvent volatilizees completely, irradiation at 40 DEG C 100mJ/cm²Ultraviolet, formed film (cured film).For the cured film, by following evaluation methods, to low-temperature bending (flexibility), grip, hot water resistance, heat resistance are evaluated.Show the result in table 2, table 3.

(evaluation method)

(1) operability

Operability to carbamate resins solution of the gained containing unsaturated group is evaluated with following 3 stage.Make With 200 μm of applicators, application is carried out with application speed 5cm/s, with the outward appearance after the just application of 3 Phase Evaluations.Will smooth and light Sliding situation is denoted as " ◎ ", visible concavo-convex situation and is denoted as "×", the situation of its intermediateness being denoted as "○", and " ◎ " "○" is remembered Make qualified.

(2) low temperature fluidity

Carbamate resins solution of the gained containing unsaturated group is stood into the fluidity after 1 week with following 3 at -5 DEG C Stage is evaluated." ◎ " is denoted as, be liquid but confirms muddy, floating material by liquid and without muddiness, the situation of floating material Situation be denoted as "○", situation about have cured is denoted as "×", it is qualified that " ◎ " is denoted as.

(3) low-temperature bending (flexibility)

Based on JIS K 6542, the test film cut out from gained cured film is implemented into the bending of 25000 times with -10 DEG C, with 3 Phase Evaluation outward appearance below.The situation that situation unconfirmed to change in test film is denoted as remaining after " ◎ ", bending is denoted as "○", the situation of test film rupture are denoted as "×", and it is qualified that " ◎ " is denoted as.

(4) grip

Horizontal platform is fixed on as upside using the cured film obtained in PET base material.Mounting half in the cured film Footpath 10mm circular counterweight (1g), during sloping platform, is obtained the angle (θ) that counterweight is skidded off, is evaluated with following 3 stage.By θ >30 ° are denoted as " ◎ ", 15 °≤θ≤30 ° and are denoted as "○", θ<15 ° are denoted as "×", and it is qualified that " ◎ " is denoted as.

(5) hot water resistance

Gained cured film and distilled water are put into sample bottle, 2 weeks are stood with 80 DEG C, with following 2 Phase Evaluation cured film Outward appearance.Situation about not changing before and after the test is denoted as lysed situation after " ◎ ", experiment and is denoted as "×", " ◎ " is remembered Make qualified.

(6) heat resistance

Gained cured film is stood 2 weeks with 110 DEG C, with the outward appearance of following 2 Phase Evaluation cured film.

Situation about not changing before and after the test is denoted as lysed situation after " ◎ ", experiment and is denoted as "×", by " ◎ " It is qualified to be denoted as.

Embodiment 7~13 and comparative example 7~12.

By the species and quality of the composition put into the 2L four-hole boiling flasks for possessing thermometer, cooling tube, agitating device such as Changed like that shown in table 2, table 3, in addition, the carbamate containing unsaturated group is manufactured similarly to Example 6 Resin, is identically formed film (cured film) and is evaluated.Show the result in table 2, table 3.

[table 2]

[table 3]

Production Example 13.

(manufacture 13 of PCDL)

In the reaction unit for being assembled with mixer, thermometer, heater, destilling tower, according to being used as the 1,6- of glycol The compounding ratio of hexylene glycol (following brief note make " 1,6-HG ") and diethyl carbonate (following brief note makees " DEC ") with molar ratio computing into For 1.08 mode, 1,6-HG 830g, DEC 771g are put into, and further put into the tetrabutyl titanium as catalysts Acid esters (following brief note makees " TBT ") 0.05g, slowly makes temperature rise to 190 DEG C under stream of nitrogen gas.Change is distillated in ethanol At the time of the tower top temperature of slow and destilling tower is changed into less than 50 DEG C, reaction temperature is kept for 190 DEG C and unchangeably slowly subtracted Straightening further makes it react 7 hours to 1.3kPa with 1.3kPa pressure.Further existed with 190 DEG C of reaction temperature It is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 (mg-KOH/g) under below 1.3kPa decompression, had The PCDL (p1) of construction unit shown in above-mentioned general formula D (following brief note makees PCD (p1)).

Production Example 14.

(manufacture 14 of PCDL)

Polycaprolactone glycol (c1) (Daicel by PCD (p1) 850g, with the construction unit shown in above-mentioned formula C Corporation systems, hydroxyl value 56.1 (mg-KOH/g).Below brief note make " PCL (c1) ") 150g at 190 DEG C, carry out 5 hours Ester exchange reaction, obtains PCDL (Polyol-22).Polyol-22 is PCL (c1)/PCD (p1)=15/85 (mol Than), hydroxyl value be 56.1mg-KOH/g (number-average molecular weight (following Mn)=2000).

Production Example 15.

(manufacture 15 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 using the manufacture method same with Production Example 13 (mg-KOH/g) PCD (p1), is obtained.

Then by PCD (p1) 700g, PCL (c1) 300g with the construction unit shown in above-mentioned formula C at 190 DEG C, 5 hours ester exchange reactions are carried out, PCDL (Polyol-23) is obtained.Polyol-23 be PCL (c1)/PCD (p1)= 30/70 (mol ratios), hydroxyl value are 56.1mg-KOH/g (Mn=2000).

Production Example 16.

(manufacture 16 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 110~114 using the manufacture method same with Production Example 13 (mg-KOH/g), obtaining the PCDL (p2) with the construction unit shown in above-mentioned general formula D, (following brief note makees PCD (p2))。

Then by PCD (p2) 700g, the polycaprolactone glycol (c2) with the construction unit shown in above-mentioned formula C (Daicel Corporation systems, hydroxyl value 112.2 (mg-KOH/g).Below brief note make " PCL (c2) ") 300g at 190 DEG C, 5 hours ester exchange reactions are carried out, PCDL (Polyol-24) is obtained.Polyol-24 be PCL (c2)/PCD (p2)= 30/70 (mol ratios), hydroxyl value are 112.2mg-KOH/g (Mn=1000).

Production Example 17.

(manufacture 17 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant is changed into 35~40 using the manufacture method same with Production Example 13 (mg-KOH/g), obtaining the PCDL (p3) with the construction unit shown in above-mentioned general formula D, (following brief note makees PCD (p3))。

Then by PCD (p3) 700g, the polycaprolactone glycol (c3) with the construction unit shown in above-mentioned formula C (Daicel Corporation systems, hydroxyl value 37.4 (mg-KOH/g).Below brief note make " PCL (c3) ") 300g at 190 DEG C, enter 5 hours ester exchange reactions of row, obtain PCDL (Polyol-25).Polyol-25 is PCL (c3)/PCD (p3)=30/ 70 (mol ratios), hydroxyl value are 37.4mg-KOH/g (Mn=3000).

Production Example 18.

(manufacture 18 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant is changed into 26~30 using the manufacture method same with Production Example 13 (mg-KOH/g), obtaining the PCDL (p4) with the construction unit shown in above-mentioned general formula D, (following brief note makees PCD (p4))。

Then by PCD (p4) 700g, the polycaprolactone glycol (c4) with the construction unit shown in above-mentioned formula C (Daicel Corporation systems, hydroxyl value 28.0 (mg-KOH/g).Below brief note make " PCL (c4) ") 300g at 190 DEG C, enter 5 hours ester exchange reactions of row, obtain PCDL (Polyol-26).Polyol-26 is PCL (c4)/PCD (p4)=30/ 70 (mol ratios), hydroxyl value are 28.2mg-KOH/g (Mn=4000).

Production Example 19.

(manufacture 19 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 using the manufacture method same with Production Example 13 (mg-KOH/g) PCD (p1), is obtained.

Then PCD (p1) 600g, PCL (c1) 400g are obtained into poly- carbonic acid at 190 DEG C, 5 hours ester exchange reactions of progress Esterdiol (Polyol-27).Polyol-27 is that PCL (c1)/PCD (p1)=40/60 (mol ratios), hydroxyl value are 56.1mg-KOH/g (Mn=2000).

Production Example 20.

(manufacture 20 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 using the manufacture method same with Production Example 13 (mg-KOH/g) PCD (p1), is obtained.

Then PCD (p1) 400g, PCL (c1) 600g are obtained into poly- carbonic acid at 190 DEG C, 5 hours ester exchange reactions of progress Esterdiol (Polyol-28).Plyol-28 is that PCL (c1)/PCD (p1)=60/40 (mol ratios), hydroxyl value are 56.1mg-KOH/g (Mn=2000).

Production Example 21.

(manufacture 21 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 using the manufacture method same with Production Example 13 (mg-KOH/g) PCD (p1), is obtained.

Then PCD (p1) 200g, PCL (c1) 800g are obtained into poly- carbonic acid at 190 DEG C, 5 hours ester exchange reactions of progress Esterdiol (Polyol-29).Polyol-29 is that PCL (c1)/PCD (p1)=80/20 (mol ratios), hydroxyl value are 56.1mg-KOH/g (Mn=2000).

Production Example 22.

(manufacture 22 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant is changed into 35~40 using the manufacture method same with Production Example 13 (mg-KOH/g) PCDL (Polyol-30) with the construction unit shown in above-mentioned general formula D, is obtained.Polyol-30 Hydroxyl value be 37.4mg-KOH/g (Mn=3000), without the construction unit shown in above-mentioned formula C.

Production Example 23.

(manufacture 23 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 using the manufacture method same with Production Example 13 (mg-KOH/g) PCDL (Polyol-31) with the construction unit shown in above-mentioned general formula D, is obtained.Polyol-31 Hydroxyl value be 56.1mg-KOH/g (Mn=2000), without the construction unit shown in above-mentioned formula C.

Production Example 24.

(manufacture 24 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 110~114 in the manufacture method same with Production Example 13 (mg-KOH/g) PCDL (Polyol-32) with the construction unit shown in above-mentioned general formula D, is obtained.Polyol-32 Hydroxyl value be 112.2mg-KOH/g (Mn=1000), without the construction unit shown in above-mentioned formula C.

Production Example 25.

(manufacture 25 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant is changed into 220~230 using the manufacture method same with Production Example 13 (mg-KOH/g), obtaining the PCDL (p5) with the construction unit shown in above-mentioned general formula D, (following brief note makees PCD (p5))。

Then by PCD (p5) 700g and the polycaprolactone glycol (c5) with the construction unit shown in above-mentioned formula C (Daicel Corporation systems, hydroxyl value 224.0 (mg-KOH/g).Below brief note make " PCL (c5) ") 300g at 190 DEG C, 5 hours ester exchange reactions are carried out, PCDL (Polyol-33) is obtained.Polyol-33 be PCL (c5)/PCD (p5)= 30/70 (mol ratios), hydroxyl value are 224.0mg-KOH/g (Mn=500).

Production Example 26.

(manufacture 26 of PCDL)

It is lasting to carry out reaction until the hydroxyl value of reactant reaches 54~58 using the manufacture method same with Production Example 13 (mg-KOH/g) PCD (p1), is obtained.

Then PCD (p1) 100g, PCL (c1) 900g are obtained into poly- carbonic acid at 190 DEG C, 5 hours ester exchange reactions of progress Esterdiol (Polyol-34).Polyol-34 is that PCL (c1)/PCD (p1)=90/10 (mol ratios), hydroxyl value are 56.1mg-KOH/g (Mn=2000).

Production Example 27.

(manufacture 27 of PCDL)

As glycol, using 1,5-PD and 1,6-HG, in addition, the manufacture method same with Production Example 1 is utilized Manufacture PCDL.Now, 1,5-PD/1,6-HG=5/5 (mol ratio) is set to, the total amount of above-mentioned glycol is used as Compounding ratio relative to DEC, 1.07, input 1,5-PD 385g, 1,6-HG 436g, DEC are turned into molar ratio computing 814g, reacts it, thus obtains PCDL (Polyol-35).Polyol-35 hydroxyl value is 56.1mg-KOH/g (Mn=2000), without the construction unit shown in above-mentioned formula C.

It should be noted that in following comparative example, as Polyol-36, using Daicel Chemical Industries, Ltd., PCL-220 (polycaprolactone glycol, hydroxyl value 56.1mg-KOH/g (Mn=2000)) processed.In addition, conduct Polyol-37, uses Baotugu Chemical Industrial Co., Ltd PTG-2000SN (polytetramethylene glycol, hydroxyl value 56.1mg- KOH/g (Mn=2000)).

Embodiment 14.

(manufacture of the polyurethane resin containing unsaturated group)

Polyol-22428.7g, different Buddhist are put into the 2L four-hole boiling flasks for being assembled with mixer, thermometer, heater Your ketone diisocyanate (following brief note makees " IPDI ") 52.9g, tin dilaurate dioctyl tin (following brief note makees DOTDL) 0.2g, With MEK (following brief note makees MEK) 500g, stir about reacts it in 12 hours at 70 DEG C.

Afterwards, input 2-hydroxyethyl methacrylate (following brief note makees HEMA) 12.7g, stir about 12 is small at 70 DEG C When react it.

Isocyanate residue is not observed by infrared absorption spectrum, thus terminated as reaction.In this way, being contained It is used as 50 mass % of solid constituent number-average molecular weight 30000, degree of unsaturation 0.20mol/kg gathering containing unsaturated group The resin solution of urethane resin.For gained resin solution, evaluated for operability and low temperature fluidity.Show the result in table 4th, table 5.

(being made using the film of active energy ray-curable resin composition)

Relative to the mass parts of polyurethane resin solid constituent 100 containing unsaturated group in gained resin solution, add Photoepolymerizationinitiater initiater (Ciba Sepcial chemicals Ltd. IRGACURE 184, the 1- hydroxy cyclohexylphenyls of 1.5 mass parts Base-phenyl ketone), the resin combination is coated on processing release paper (for folder by resin composition modulation with about 200 μm of thickness The evaluation of holding property, uses PET base material).Afterwards, placed 24 hours at 40 DEG C, make after organic solvent volatilizees completely, to irradiate 100mJ/ cm²Ultraviolet, formed film (cured film).It is (soft to low-temperature bending by following evaluation methods for the cured film Property), grip, heat resistance evaluated.Show the result in table 4, table 5.

(evaluation method)

(1) operability

Operability for polyurethane resin solution of the gained containing unsaturated group is evaluated with following 3 stage.

Using 200 μm of applicators, application is carried out with application speed 5cm/s, the outward appearance after just application is carried out with 3 stages Evaluate.Smooth and smooth situation is denoted as into " ◎ ", visible concavo-convex situation it is denoted as "×", situation in the middle of it being denoted as "○".

(2) low temperature fluidity

To polyurethane resin solution of the gained containing unsaturated group is stood into the fluidity after 1 week at -5 DEG C with following 3 rank Duan Jinhang is evaluated." ◎ " is denoted as, be liquid but confirms muddy, floating material by liquid and without muddiness, the situation of floating material The situation that situation is denoted as "○", have cured is denoted as "×".

(3) low-temperature bending (flexibility)

Based on JIS K 6542, the test film cut out from gained cured film is implemented into the bending of 25000 times with -30 DEG C, it is right Outward appearance is evaluated with following 3 stage.The situation that change is not confirmed in test film is denoted as situation about being remained after " ◎ ", bending It is denoted as "○", the situation of test film rupture and is denoted as "×".

(4) grip

Horizontal platform is fixed on as upside using the cured film obtained in PET base material.Mounting half in the cured film Footpath 10mm circular counterweight (1g), during sloping platform, is obtained the angle (θ) that counterweight is skidded off, is evaluated with following 3 stage.By θ >30 ° are denoted as " ◎ ", 15 °≤θ≤30 ° and are denoted as "○", θ<15 ° are denoted as "×".

(5) heat resistance

Gained cured film is stood 2 weeks with 110 DEG C, the outward appearance to cured film is evaluated with following 2 stage.

The situation without change is denoted as lysed situation after " ◎ ", experiment and is denoted as "×" before and after testing.

Embodiment 15~21 and comparative example 13~20.

By the species and quality of the composition put into the 2L four-hole boiling flasks for possessing thermometer, cooling tube, agitating device such as Changed like that shown in table 4, table 5, in addition, the polyurethane resin containing unsaturated group manufactured similarly to Example 1, It is identically formed film (cured film) and is evaluated.Result is shown in table 4, table 5 in the lump.

[table 4]

[table 5]

In detail and the present invention is described with reference to specific embodiment, but to those skilled in the art, It is readily apparent that in the case where not departing from the spirit and scope of the present invention, various changes, amendment can be subject to.

It should be noted that by Japan's patent application filed in 6 days 2015-022265 in 2 months in 2015,2015 years 3 Japan's patent application 2015-050055 filed in months 12 days, Japan's patent application filed in 10 days June in 2015 The specification of No. 2015-117378, claims, the full content of accompanying drawing and summary are quoted so far, are used as saying for the present invention The disclosure of bright book and be introduced into.

Claims (18)

1. a kind of coating urethane resin compositions, it is to include polyalcohol (A), polyisocyanates (B) and delustering agent (D) polyurethane resin composition, it is characterised in that polyalcohol (A) includes PCDL (a1) and hydroxy functional group number For more than 3 PEPA (a2), the average hydroxyl functional group number of polyalcohol (A) be 2.3~3.5, hydroxyl value be 70~ 285mgKOH/g, and the mass ratio of (a1) and (a2) is (a1)/(a2)=75/25~55/45.

2. coating urethane resin compositions according to claim 1, it is characterised in that polyalcohol (A) is included： The PEPA (a2) and hydroxy functional group number that PCDL (a1), hydroxy functional group number are more than 3 be more than 2 and PEPA (a3) less than 3.

3. the coating urethane resin compositions according to claim 1 or claim 2, it is characterised in that poly- Ester polyol (a2), (a3) are PEPAs obtained from by making cyclic ester compounds progress ring opening polyaddition.

4. the coating urethane resin compositions according to any one of claim 1 to claim 3, its feature It is, polyisocyanates (B) includes the tripolymer of aliphatic isocyanates.

5. the coating urethane resin compositions according to any one of claim 1 to claim 4, wherein, Delustering agent (D) contains selected from least one of group being made up of inorganic micro powder body and organic micropowder body.

6. the coating urethane resin compositions according to any one of claim 1 to claim 4, its feature It is, delustering agent (D) is silica.

7. a kind of feel coating, it is comprising the coating any one of claim 1 to claim 6 with carbamate tree Oil/fat composition.

8. a kind of active energy ray-curable resin composition, its be comprising polyalcohol (A), (methyl) acrylate (a6) and The polyurethane resin composition of polyisocyanates (B), it is characterised in that polyalcohol (A) is selected from by including 3- methyl isophthalic acids, 5- penta Glycol as monomeric unit PCDL (a4) and include the makrolon two of the construction unit shown in following formula A At least one of group of alcohol (a5) composition, (methyl) acrylate (a6) includes more than 1 hydroxyl and more than 1 (methyl) third Enoyl-,

9. active energy ray-curable resin composition according to claim 8, it is characterised in that the makrolon The number-average molecular weight of glycol (a4) is 300~5000 scope.

10. active energy ray-curable resin composition according to claim 8, it is characterised in that the poly- carbonic acid Esterdiol (a5) includes the construction unit shown in following formula A and the construction unit shown in following Formula Bs,

In formula, R is separately divalent alkyl, and optionally with substituent, the carbon atom of more than 1 in the alkyl is optional Replaced by divalent aromatic group, divalent hetero ring type base or divalent crosslinking carbocylic radical, 1 in addition to end in the alkyl Carbon atom above is optionally replaced by oxygen atom or sulphur atom.

11. the active energy ray-curable resin composition according to claim 8 or claim 10, its feature exists In the PCDL (a5) is the chemical combination for including the structure shown in the structure and following general formula Ds shown in following formula C Thing, contains the structure shown in following formula C and the knot shown in following general formula Ds with the ratio of n/m=80/20~5/95 (mol ratio) Structure,

In formula, R is separately divalent alkyl, and optionally with substituent, the carbon atom of more than 1 in the alkyl is optional Replaced by divalent aromatic group, divalent hetero ring type base or divalent crosslinking carbocylic radical, 1 in addition to end in the alkyl Carbon atom above is optionally replaced by oxygen atom or sulphur atom, n >=1, m >=1.

12. the active energy ray curable tree according to any one of claim 8, claim 10 or claim 11 Oil/fat composition, it is characterised in that the number-average molecular weight of the PCDL (a5) is 800~5000 scope.

13. the active energy ray-curable resin composition according to any one of claim 8 to claim 12, its It is characterised by, the molecular weight of (methyl) acrylate (a6) is 100~3000 scope.

14. the active energy ray-curable resin composition according to any one of claim 8 to claim 13, its Be characterised by, (methyl) acrylate (a6) be selected from by acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, The 6-caprolactone addition product of acrylic acid 2- hydroxy methacrylates, Beta-methyl-valerolactone addition product of acrylic acid 2- hydroxy methacrylates, methyl-prop The 6-caprolactone addition product of olefin(e) acid 2- hydroxy methacrylates and the Beta-methyl of 2-hydroxyethyl methacrylate-valerolactone addition product composition Group in it is at least one kind of.

15. the active energy ray-curable resin composition according to any one of claim 8 to claim 14, its It is characterised by, the polyisocyanates (B) is selected from the group being made up of aliphatic diisocyanate and alicyclic diisocyanate In it is at least one kind of.

16. the active energy ray-curable resin composition according to any one of claim 8 to claim 15, its Be characterised by, the number-average molecular weight of the polyurethane resin composition be 1000~200000 and degree of unsaturation be 0.1~ 1mol/kg。

17. the active energy ray-curable resin composition according to any one of claim 8 to claim 16, its It is characterised by, also containing drawing relative to the mass parts of polyurethane resin composition 100 for the photopolymerization of 0.01~15 mass parts Send out agent.

18. a kind of coating, it is as the active energy ray curable tree any one of claim 8 to claim 17 Oil/fat composition formation.