TW201422665A - Polyester polycarbonate polyol - Google Patents

Abstract

Provided is a polyester polycarbonate polyol, which can obtain a coating film having excellent adhesiveness by using polyurethane resin or urethane acrylate or the like as raw materials. The present invention provides a polyester polycarbonate polyol, as well as a polyurethane resin and urethane acrylate obtained by using the same. The polyester polycarbonate polyol contains a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and a hydroxyl group in an end of molecule end, wherein the repeating unit represented by the formula (1) contains two or more repeating units represented by the formula (3).

Description

Polyester polycarbonate polyol

The present invention relates to a polyester polycarbonate polyol, and a polyurethane resin obtained using the same, and a urethane acrylate.

The polycarbonate diol can be used as a raw material of a polyurethane resin, a urethane acrylate, a thermoplastic elastomer or the like, wherein 1,6-hexanediol and 1,4-butanediol or A polycarbonate diol obtained by copolymerization of 1,5-pentanediol can be used as a raw material to obtain a polyurethane resin having a balance between hydrolysis resistance, light resistance, oxidation resistance, and elastic recovery property (Patent Document 1). .

In recent years, in order to improve the polymerization reactivity in the reaction for producing a polyurethane resin or the like, a technique for controlling the first-order terminal OH ratio of the polycarbonate diol has been proposed (Patent Documents 2 to 4).

Advanced technical literature (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. Hei 2-289616

Patent Document 2: Patent No. 3874664

Patent Document 3: WO2009/063767

Patent Document 4: WO2009/063768

However, in the coating composition using the polycarbonate diol of the above prior art, depending on the object to be coated, there is a problem that the resulting coating film cannot be adhered and is easily peeled off. Especially for synthetic rubbers such as ethylene-propylene-diene rubber (EPDM), the problem of adhesion is more pronounced. An object of the present invention is to provide a material for a coating film which can solve the problem and which is excellent in adhesion.

The present inventors have found that the repeating unit represented by the formula (2) can be introduced into a polycarbonate polyol in a specific amount to form a polyester polycarbonate polyol, whereby the above problems can be solved, and the present invention has been completed.

(In the formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms)

The present invention relates to a polyester polycarbonate polyol comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a hydroxyl group at a molecular terminal, wherein The repeating unit represented by the formula (1) contains two or more kinds of repeating units represented by the following formula (3).

(In the formula (1), R ¹ represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(In the formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(In the formula (3), n represents an integer of 2 to 20.)

The present invention relates to a polyester polycarbonate polyol according to the first aspect of the invention, wherein the amount of the repeating unit represented by the formula (2) is 1 in the total of the repeating units represented by the formula (1) and the formula (2). Up to 60% by mole.

The present invention relates to a polyester polycarbonate polyol according to the invention 1 or 2, wherein the amount of the repeating unit represented by the formula (3) is 60 to 100 mol% in the repeating unit represented by the formula (1) .

The polyester polycarbonate polyol according to any one of the inventions 1 to 3, wherein the repeating unit represented by the formula (3) is a repeating unit represented by the formulae (4) to (7). Two or more selected in the group.

The present invention relates to a polyester polycarbonate polyol according to the invention 4, wherein the repeating unit represented by the formula (3) is a repeating unit represented by the formula (5) and the formula (7).

The invention relates to a polyester polycarbonate polyol according to the invention 5, wherein the amount of the repeating unit represented by the formula (5) is from 30 to 95 in the repeating unit represented by the formula (5) and the formula (7). Moer%.

The present invention relates to a polyester polycarbonate polyol according to the fourth aspect of the invention, wherein the repeating unit represented by the formula (3) is a repeating unit represented by the formula (6) and the formula (7).

The present invention relates to a polyester polycarbonate polyol according to the seventh aspect of the invention, wherein the amount of the repeating unit represented by the formula (6) is from 20 to 80 in the repeating unit represented by the formula (6) and the formula (7). Moer%.

The polyester polycarbonate polyol according to any one of the inventions 1 to 8, wherein the repeating unit represented by the formula (2) is a repeat represented by the formulas (4') to (7') One or more selected from the group of cells.

The present invention relates to a polyester polycarbonate polyol according to the invention 9, wherein the repeating unit represented by the formula (2) is a repeating unit represented by the formula (6').

The polyester polycarbonate polyol according to any one of the inventions 1 to 10, wherein the number average molecular weight is from 500 to 5,000.

The present invention relates to a polyurethane resin obtained by copolymerizing a polyester polycarbonate polyol according to any one of Inventions 1 to 11 with a polyvalent isocyanate.

The present invention relates to a urethane acrylate obtained by reacting the polyester polycarbonate polyol, the polyvalent isocyanate, and the hydroxyl group-containing (meth) acrylate of any one of the inventions 1 to 11.

Making the polyester polycarbonate polyol of the present invention as a polyamine A material such as a formate resin or a urethane acrylate can be used to obtain a coating film having excellent adhesion. The polyester polycarbonate polyol according to the present invention, particularly for a synthetic rubber such as ethylene-propylene-diene rubber (EPDM), can provide excellent coating film adhesion.

The polyester polycarbonate polyol of the present invention contains a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and a hydroxyl group at the molecular terminal.

In the present invention, the repeating unit represented by the formula (1) is as follows.

(In the formula (1), R ¹ represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

In the present invention, the repeating unit represented by the formula (1) contains two or more kinds of repeating units represented by the formula (3). The number of repeating units represented by the formula (3) may be 2 to 5, and from the viewpoint of easily controlling the physical properties of the polyester polycarbonate polyol, it is preferably 2 or 3 kinds.

In the present invention, the repeating unit represented by the formula (3) is as follows.

(In the formula (3), n represents an integer of 2 to 20.)

The amount of the repeating unit represented by the formula (3) is 60 mol% or more in the repeating unit represented by the formula (1), and is preferable in terms of lowering the viscosity and being easy to handle. The amount is preferably 90 mol% or more, more preferably 100 mol%, and the repeating unit represented by the formula (1) may be all repeating units represented by the formula (3).

The repeating unit represented by the formula (3) may be a repeating unit represented by the formulae (4) to (7), and may be two or more of these.

For example, the repeating unit represented by the formula (3) may be combined with the repeating unit represented by the formula (5) and the formula (7). This combination is used as a combination of a polyurethane resin and the like. When forming a raw material of a resin, it is preferable from the viewpoint of easily obtaining solvent resistance from a synthetic resin.

In the combination, the amount of the repeating unit represented by the formula (5) may be 30 to 95 mol% in the repeating unit represented by the formula (5) and the formula (7). If it is in this range, it is expected that the polyester polycarbonate polyol has fluidity (for example, viscosity of 500 to 7000 cP) at room temperature (25 ° C) or under heating (for example, heating to 55 ° C). The amount is preferably from 51 to 95 mol%, more preferably from 60 to 95 mol%. Here, the viscosity is an E-type viscometer ("BROOLFIELD viscometer LV DV-II+Pro" manufactured by BROOKFIELD Co., Ltd.), and the value measured at a fixed temperature is as follows.

When the viscosity is 300 to 1900 cP: the cone plate is made of "Spindle CPE-42" and the value measured by the number of revolutions of 0.3 rpm is used as the viscosity.

When the viscosity is 1901 to 4000 cP: the cone plate is made of "Spindle CPE-52" and the value measured by the number of rotations of 0.6 rpm is used as the viscosity.

When the viscosity is 4001 to 20000 cP: the cone plate is made of "Spindle CPE-52" and the value measured by the number of revolutions of 0.3 rpm is used as the viscosity.

When the viscosity is from 20001 to 60,000 cP: the cone plate is made of "Spindle CPE-52" and the value measured by the number of revolutions of 0.1 rpm is used as the viscosity.

When the viscosity is 60001 to 100000 cP: the cone plate is made of "Spindle CPE-52" and the value measured by the rotation number of 0.05 rpm is used as the viscosity.

Further, for example, as the repeating unit represented by the formula (3), the repeating unit represented by the formula (6) and the formula (7) can be combined. When the combination is used as a raw material of a synthetic resin such as a polyurethane resin, it is preferable from the viewpoint that the synthetic resin can easily obtain high flexibility.

In the combination, the amount of the repeating unit represented by the formula (6) may be 20 to 80 mol% in the repeating unit represented by the formula (6) and the formula (7). If it is in this range, it is expected that the polyester polycarbonate polyol has fluidity (for example, viscosity of 500 to 7000 cP) at room temperature (25 ° C) or under heating (for example, heating to 55 ° C). The amount is more preferably from 30 to 70 mol%, particularly preferably more than 50 mol%, and 70 mol% or less.

Further, for example, as the repeating unit represented by the formula (3), a combination of the repeating unit represented by the formula (4), the formula (5) and the formula (7), or the formula (4) or the formula (6) may be used. And a combination of the repeating unit shown in the formula (7).

As a repeating unit represented by the formula (1) other than the formula (3), R ¹ may be a branched alkyl group having a carbon number of 2 to 20, for example, a propyl group, an isobutylene group or a 2-methyl group. Methyl, 2-methylpentamethylene, 3-methylpentamethylene, iso-n-methylene, 2-methylhexamethylene, etc.; substituted or unsubstituted ring extension of carbon number 3 to 20. An alkyl group, for example, a cyclopentyl group, a cyclohexyl group, a 1,2-dimethylenecyclopentyl group, a 1,3-dimethylenecyclopentyl group, a 1,2-dimethylene ring Alkyl, 1,3-dimethylenecyclohexane, 1,4-dimethylenecyclohexane, 4,4'-methylenebicyclohexylene, 2,2-dicyclohexyl a propane group or the like; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, such as a phenyl group, a 1,2-dimethylene phenyl group, a 1,3-dimethylene phenyl group, or 1,4- A repeating unit such as a dimethylenephenyl group, an anthranyl group, a 4,4'-methylenediphenylene group, or a 2,2-diphenylenepropanyl group.

In the present invention, the repeating unit represented by the formula (2) is as follows.

(In the formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

R ² may, for example, be a linear or branched alkyl group having 2 to 20 carbon atoms, such as an ethyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group or a heptamethylene group. , octamethylene, hexamethylene, propyl, isobutyl, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, iso-jaya a methyl group, a 2-methylhexamethylene group or the like; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and a 1,2-dimethylene cyclopentane. Base, 1,3-dimethylenecyclopentyl, 1,2-dimethylenecyclohexane, 1,3-dimethylenecyclohexane, 1,4-dimethylene ring Hexyl group, 4,4'-methylenebicyclohexylene group, 2,2-dicyclohexylpropane group, etc.; substituted or unsubstituted aryl group having 6 to 20 carbon atoms, for example, phenyl group, 1 , 2-dimethylenephenyl, 1,3-dimethylenephenyl, 1,4-dimethylenephenyl, anthranyl, 4,4'-methylenediphenyl, 2 a repeating unit such as 2-diphenylpropanyl.

R ^{2 is} preferably a linear alkyl group having 2 to 20 carbon atoms, and may be a repeating unit represented by the formulae (4') to (7'), and may be one or more of these.

Among them, the formula (6') is preferred in view of ease of obtaining raw materials.

The amount of the repeating unit represented by the formula (2) may be 1 to 60 mol% in the total of the repeating units represented by the formulas (1) and (2). If it is in this range, the fluidity (for example, viscosity of 500 to 7000 cP) at room temperature (25 ° C) or under heating (for example, heating to 55 ° C) can be more easily obtained while maintaining hydrolysis resistance. The amount is preferably from 2 to 50 mol%, more preferably from 3 to 30 mol%.

In the present invention, the form of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is not particularly limited, and may be a random or a block. The mode of existence of the repeating unit represented by the formula (3) contained in the repeating unit represented by the formula (1) is also not particularly limited, and may be random or block.

In the polyester polycarbonate polyol of the present invention, the number average molecular weight Mn may be from 500 to 5,000. If it is in this range, fluidity (for example, viscosity of 500 to 7000 cP) at room temperature (25 ° C) or heating (for example, 55 ° C) can be easily obtained, and the handleability is excellent. The number average molecular weight Mn is preferably from 500 to 3,500, more preferably from 500 to 3,000. In the present specification, the number average molecular weight Mn is a hydroxyl value measured according to JIS K 1577, and based on the hydroxyl value Calculated number average molecular weight. Specifically, the hydroxyl value is measured and calculated by the terminal group quantitative method using (56.1 × 1000 × valence) / hydroxyl number (in the formula, the hydroxyl group unit is [mgKOH / g]). In the above formula, the valence number is the number of hydroxyl groups in one molecule.

In the polyester polycarbonate polyol of the present invention, the weight average molecular weight Mw may be from 500 to 15,000. The weight average molecular weight Mw is preferably from 1,000 to 13,000. In the present specification, the weight average molecular weight Mw is a value measured by GPC.

In the polyester polycarbonate polyol of the present invention, the degree of dispersion Mw/Mn may be from 1.0 to 3.0. The degree of dispersion Mw/Mn is preferably from 2.0 to 2.3.

In the polyester polycarbonate polyol of the present invention, the acid value may be from 0 to 1 mgKOH/g. When it is this range, it can obtain the polyurethane resin which is especially favorable in physical property. The acid value is preferably from 0 to 0.1 mgKOH/g, more preferably from 0 to 0.05 mgKOH/g. In the present specification, the acid value is a value measured according to the indicator titration method of JIS K 1557.

The present invention has a hydroxyl group at the molecular end. The present invention is preferably a polyester polycarbonate diol having a hydroxyl group at the ends of two molecules.

The present invention may contain repeating units (other repeating units) other than the repeating units represented by the formulas (1) and (2). The other repeating unit is preferably 10 mol% or less, more preferably 5 mol% or less in the repeating unit of the present invention.

The other repeating unit may be a repeating unit derived from a polybutadiene polyol or the like.

In the present invention, the ratio of the number of moles of the repeating unit represented by the formula (1) or (2) in the repeating unit or the repeating unit represented by the formula (3) may be Conversion of the raw materials consumed by the polyester polycarbonate polyol of the present invention. Specifically, it can be determined from the ratio of the number of moles of the raw material added to the production of the polyester polycarbonate polyol. However, in the production step, when the raw material diol is distilled, it is obtained by subtracting the distilled raw material diol.

The method for producing the polyester polycarbonate polyol of the present invention is not particularly limited, and examples thereof include a method of reacting the glycol of the corresponding formula (1), the lactone of the corresponding formula (2), and a carbonate. In this method, the temperature at the time of the reaction may be from 50 to 250 ° C, preferably from 70 to 220 ° C. The pressure during the reaction may be from 0 to 1000 mmHg, preferably from 0.1 to 760 mmHg. The reaction time can be from 5 to 48 hours.

The reaction is preferably carried out by discharging the alcohol of the by-product out of the system. At this time, in the case where the carbonate is azeotroped with the alcohol of the by-product and discharged to the outside of the system, an excess amount of the carbonate can be added.

The reaction may be carried out using a catalyst or without using a catalyst. When a catalyst is used, a catalyst used in a known transesterification reaction can be mentioned, and for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, lanthanum can be used. a metal such as tin, lead, antimony, arsenic or antimony or a salt, alkoxide or organic compound thereof. Particularly preferred are compounds of sodium, titanium, zirconium, tin, etc., such as sodium hydride, titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium acetonate, zirconium oxyacetate, dibutyltin dilaurate, Dibutyltin dimethoxide, dibutyltin oxide, and the like. The amount of the catalyst used is preferably from 1 to 20,000 ppm by weight, more preferably from 10 to 5,000 ppm by weight, particularly preferably from 20 to 4,000 ppm by weight, based on the total amount of the polyester polycarbonate polyol.

After completion of the reaction, the unreacted glycols and lactones are distilled off as needed, whereby the polyester polycarbonate polyol of the present invention can be obtained.

The glycol of the repeating unit represented by the formula (1) may, for example, be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol or 1,6-hexane. Alcohol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-tweldium An alkanediol or the like which does not have a side chain having 2 to 20 carbon atoms. These diols may be a repeating unit represented by the formula (3), and two or more kinds thereof may be used.

Further, examples of the diols include 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, and 3-methyl group. -1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl - alkanediol having 2 to 20 carbon atoms having a side chain such as 1,3-propanediol or 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol; Cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl)cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, 2,7-norbornane a diol such as a diol having an alicyclic structure of 6 to 20 carbon atoms; 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 2,7-naphthalene A diol or the like having an aromatic ring structure having a carbon number of 6 to 20, such as methanol.

Further, a polyhydric alcohol such as trimethylolpropane, neopentyltetraol or sorbitol may be used.

The lactones of the repeating unit represented by the formula (2) may, for example, be ω-lactone, β-propiolactone, β-butyrolactone, β-valerolactone, δ-valerolactone, β-A. Base-δ-valerolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, ω-heptanolactone, ω-octanolactone, ω-laurolactone, etc. carbon The number of lactones is from 3 to 21, preferably ε-caprolactone.

Examples of the carbonates include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate; aromatic carbonates such as diphenyl carbonate; and cyclic carbonates such as ethyl carbonate; From this point of view, it is preferably an aliphatic carbonate or a cyclic carbonate, particularly preferably dimethyl carbonate or ethyl carbonate.

The polyester polycarbonate polyol of the present invention can be used as a raw material for a polyurethane, a urethane acrylate or the like, a coating agent, an additive for a coating or an ink, and the like.

The polyester polycarbonate polyol of the present invention and a polyvalent isocyanate are reacted to obtain a polyurethane resin.

The polyvalent isocyanate which can be used in the production of the polyurethane resin of the present invention includes, for example, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, and a mixture thereof (TDI). ), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-extended biphenyl diisocyanate An aromatic diisocyanate such as crude TDI, polymethylene polyphenyl isocyanate or crude MDI; known aromatic aliphatic diisocyanate such as benzene dimethylene diisocyanate (XDI) or phenyl diisocyanate; 4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexane-1,2-diyl bis(methylene) A known aliphatic diisocyanate such as diisocyanate (hydrogenated XDI), and a trimerized modified product of the isocyanate, a carbodiimide modified product, a biuretized modified product, and the like.

In the production of the polyurethane resin of the present invention, a chain extender can be used as a copolymerization component. As the chain extender, a known chain extender can be used, and examples thereof include water, a low molecular polyol, a polyamine, and the like. For example, the chain extender can be referred to "the latest polyurethane application technology" (CMC Co., Ltd., published in 1985).

As the low molecular polyol, a diol having a molecular weight of 300 or less can be used, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. An aliphatic diol such as an alcohol, neopentyl glycol or 1,10-decanediol; a fat such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or tricyclodecane dimethanol Cyclohexane; benzenedimethanol, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy) Phenyl]anthracene, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, and the like. It is preferred to use ethylene glycol or 1,4-butanediol.

In view of the use of the polyurethane resin, a known polymer polyol can be used as the chain extender in the range which does not impair the effects of the present invention. Examples of the polymer polyol include a polyester polyol, a polyether carbonate having a polyoxyalkylene chain (polyether carbonate polyol), and the like. For example, the "polyurethane foam" (polymeric press conference, 1987) can be referred to as a polymer polyol.

The method for producing the polyurethane resin of the present invention can use a known technique of polyurethaneization reaction, for example, the polyester polycarbonate diol of the present invention and the organic polyisocyanate at room temperature (25 ° C under atmospheric pressure). The reaction is carried out at 200 ° C, whereby a polyurethane resin can be produced. When a chain extender is used, it may be added initially from the reaction or may be added from the reaction. Polyamine For the production method of the acid ester resin, for example, reference is made to U.S. Patent No. 5,070,173.

A known polymerization catalyst can be used for the polyurethaneization reaction, and examples thereof include an organic metal salt such as a tertiary amine, tin or titanium. For the polymerization catalyst, refer to pages 23 to 32 of the "Polyurethane Resin" (Japan Industrial News Corporation, 1969).

The polyurethaneization reaction can be carried out in the presence of a solvent. Examples of the solvent include dimethylformamide, diethylformamide, dimethylacetamide, dimethylhydrazine, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, and benzene. , toluene, ethyl cellosolve, etc.

A blocking agent can be used in the polyurethaneization reaction. The blocking agent is a compound containing only one active hydrogen reactive with an isocyanate group, and examples thereof include a monohydric alcohol such as ethanol or propanol, and a secondary amine such as diethylamine or di-n-propylamine. Wait.

A stabilizer such as a thermal stabilizer (for example, an antioxidant) or a light stabilizer may be blended in the polyurethane resin of the present invention. Examples of the antioxidant include aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid or phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, and polyphosphate. Phosphorus compounds such as dialkyl pentaerythritol diphosphite, dialkyl bisphenol A diphosphite; phenolic derivatives (especially hindered phenol compounds); thioether, disulfate, nonylbenzene A sulfur compound such as imidazole, diphenylthiourea or thiodipropionate; or a tin compound such as tin maleate or dibutyltin oxide.

Antioxidants can be divided into primary, secondary and tertiary anti-aging agents. The hindered phenolic compound of primary anti-aging agent is preferably Irganox1010. Product name; manufactured by BASF Corporation), Irganox 1520 (trade name; manufactured by BASF Corporation). The phosphorus-based compound of the secondary anti-aging agent is preferably PEP-36, PEP-24G, HP-10 (all of which are trade names; manufactured by Asahi Kasei Co., Ltd.) and Irgafos 168 (trade name; manufactured by BASF Corporation). Further, the sulfur compound of the third anti-aging agent is preferably a thioether compound such as dilauryl thiopropionate (DLTP) or distearyl thiopropionate (DSTP).

Examples of the photosensitizer include an ultraviolet absorbing type light stabilizer and a radical trap type light stabilizer. Examples of the ultraviolet absorbing type light stabilizer include a benzotriazole type compound and a diphenyl ketone type compound. Examples of the radical trapping type photostabilizer include hindered amine compounds and the like. These stabilizers may be used singly or in combination of two or more. The stabilizer is preferably added in an amount of from 0.01 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight, still more preferably from 0.2 to 2 parts by weight, per 100 parts by weight of the polyurethane resin.

A plasticizer may be blended in the polyurethane resin of the present invention. Plasticizers such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, citric acid Terephthalate of di(undecyl)ester, diisononyl phthalate, etc.; tricresyl phosphate, triethyl phosphate, tributyl phosphate, tris-2-ethylhexyl phosphate, trimethyl phosphate Phosphate esters such as hexyl hexyl ester, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, etc.; benzoic acid esters such as octyl benzene tricarboxylate and isodecyl benzoate; Pentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl sebacate, dioctyl sebacate, dioctyl sebacate, sebacic acid Fatty acids such as 2-ethylhexyl ester and ethyl ricinoleate Esters; benzoic acid esters such as octyl benzoate; epoxy-based plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl ester; adipic acid ether ester, polyether, etc. The polyether plasticizer is a liquid rubber such as liquid NBR, liquid acrylic rubber or liquid polybutadiene; non-aromatic paraffin oil or the like. These plasticizers may be used singly or in combination of two or more. The amount of the plasticizer to be added is appropriately selected depending on the hardness and physical properties to be obtained, but it is preferably 0.1 to 50 parts by weight per 100 parts by weight of the polyurethane resin.

Further, the polyurethane resin of the present invention may be blended with an inorganic filler, a lubricant, a colorant, an emu oil, a foaming agent, a flame retardant or the like. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, citric acid (white carbon), titanium oxide, and carbon black. These various additives can be used in an amount generally used in the conventional polyurethane resin.

The Shore D hardness of the polyurethane resin of the present invention is preferably from 20 to 70, more preferably from 25 to 50. When the Shore D hardness is 20 or more, the heat resistance and the abrasion resistance are sufficiently high, and when the Shore D hardness is 70 or less, the obtained low-temperature performance and soft feeling are not insufficient. The molecular weight of the polyurethane resin of the present invention is preferably 10,000 to 10,000 by the polystyrene-equivalent number average molecular weight (Mn) measured by GPC analysis and the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC analysis. The range of 200,000.

The polyester polycarbonate polyol of the present invention can be used as a raw material for urethane acrylate.

A urethane acrylate imparts the reactivity of the polyester polycarbonate polyol, the polyisocyanate, and the isocyanate group of the present invention The base (meth) acrylate is obtained by reaction. Specifically, the urethane acrylate type can be prepared by the method described in JP-A-6-145636 and JP-A-2003-183345.

As the polyvalent isocyanate, for example, a polyisocyanate which can be used in the production of a polyurethane resin can be used, and it is preferably from isophorone diisocyanate (IPDI), 4, 4'-di, from the viewpoint of easy handling. Cyclohexylmethane diisocyanate (hydrogenated MDI), 4,4'-diphenylene diisocyanate (MDI), methylcyclohexyl diisocyanate (hydrogenated TDI), 2,4-toluene diisocyanate (TDI One or more selected from the group.

Among the (meth) acrylates having a group reactive with an isocyanate group, a group reactive with an isocyanate group may, for example, be a hydroxyl group, an amine group or a thiol group. Specifically, a hydroxyl group-containing (meth) acrylate can be used, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Propyl ester, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-(methyl)propenyloxypropyl acrylate, 2-hydroxy-3-phenyloxy ( Methyl)acrylate, 1,4-butanediol mono(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylic acid Ester, tetramethylol methane tri(meth) acrylate, triethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone diol mono (meth) acrylate , pentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth) acrylate, and the like. Among them, in view of ease of handling, it is preferred to use 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl alcohol tri(meth)acrylate, Selected from a group of dipentaerythritol penta (meth) acrylate One or more of them.

The coating agent can be prepared by blending a photoinitiator in the urethane acrylate of the present invention and optionally blending a (meth) acrylate. As the photoinitiator, a known one may be used, and examples thereof include diphenyl ketone, substituted diphenyl ketone, acetophenone, substituted acetophenone, benzoin, benzoin, xanthone, and substituted xanthene. Ketone, phosphine oxide, diethoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxy xanthone, chloro-thioxanthone, N-methyldiethanol-amine-diphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-benzyl-2-(dimethylamino)-1 -[4-(4-Folininyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, and the like. Among them, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide is preferred from the viewpoint of reactivity and ease of handling.

The (meth) acrylate is not particularly limited, and the compounds exemplified above for the hydroxy group-containing (meth) acrylate can be used. Among them, from the viewpoint of reactivity, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and trimethylolpropane tris(methyl) are preferred. ) acrylate, neopentyl alcohol tetra (meth) acrylate, neopentyl alcohol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tetra (methyl) One or more selected from the group consisting of acrylates.

The coating agent may contain a solvent, and examples thereof include a ketone system (such as acetone or methyl ethyl ketone), an ester system (such as methyl acetate or ethyl acetate), an ether system (diethyl ether, tetrahydrofuran, etc.), and a hydrocarbon. A solvent (n-hexane, benzene, etc.).

The polyester polycarbonate polyol of the present invention can be used for polymerization A raw material such as a urethane or a urethane acrylate, or an additive for a coating agent, a coating or an ink.

Example

The invention will now be further illustrated by way of examples and comparative examples.

The number average molecular weight was measured in the following manner.

The hydroxyl value was measured in accordance with the B method of JIS K 1577. Based on the measured hydroxyl value, the number average molecular weight Mn was calculated by the following formula.

Number average molecular weight Mn = (56.1 × 1000 × 2) / hydroxyl price

The acid value was measured in accordance with the indicator titration method of JIS K 155.

For the viscosity, an E-type viscometer ("BROOLFIELD viscometer LV DV-II+Pro" manufactured by BROOKFIELD Co., Ltd.) was used, and the value measured at a fixed temperature was as follows.

When the viscosity is 300 to 1900 cP: "Spindle CPE-42" is used for the cone plate, and the value measured by the number of rotations of 0.3 rpm is used as the viscosity.

When the viscosity is 1901 to 4000 cP: "Spindle CPE-52" is used for the cone plate, and the value measured by the number of rotations of 0.6 rpm is used as the viscosity.

When the viscosity is 4001 to 20000 cP: "Spindle CPE-52" is used for the cone plate, and the value measured by the rotation number of 0.3 rpm is used as the viscosity.

When the viscosity is from 20001 to 60,000 cP: "Spindle CPE-52" is used for the cone plate, and the value measured by the number of rotations of 0.1 rpm is used as the viscosity.

When the viscosity is 60001 to 100000 cP: "Spindle CPE-52" is used for the cone plate, and the value measured by the rotation number of 0.05 rpm is used as the viscosity.

The weight average molecular weight (Mw) is a value measured by GPC and converted to polystyrene.

Further, Mw and Mn used for calculating the degree of dispersion (Mw/Mn) are also values measured by GPC and converted to polystyrene. Therefore, both the Mn used for calculating the degree of dispersion and the Mn calculated by the above valence of the hydroxyl group are different values.

The ratio of the number of moles of each repeating unit in the obtained polyester polycarbonate diol was calculated from the amount of the raw material added.

Example 1

The starting material was added in the form of 1,6-hexanediol: 1,5-pentanediol = 48:52 (mole ratio). Further, a raw material was added in such a manner that the total of 1,6-hexanediol and 1,5-pentanediol: ε-caprolactone = 9:1 (mole ratio).

In a 1000 ml glass round bottom flask equipped with a rectification column, a stirrer, a thermometer, and a nitrogen introduction tube, 350.2 g (3.89 mol) of dimethyl carbonate and 186.8 g (1.58 mol) of 1,6-hexanediol were added. 5-pentanediol 178.4g (1.71mol), ε-caprolactone 41.8g (0.37mol), titanium tetrabutoxide 0.05g, distilling off methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring The mixture of esters was subjected to a transesterification reaction for 10 hours. At this time, the reaction temperature was gradually raised from 95 ° C to 200 ° C, and the composition of the distillate was adjusted to become an azeotropic composition of methanol and dimethyl carbonate, or a composition thereof.

Thereafter, the pressure was gradually reduced to 30 mmHg, and the mixture of methanol and dimethyl carbonate was distilled off while stirring, and the transesterification reaction was further carried out at 180 ° C for 10 hours. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction liquid was cooled to room temperature to obtain 466.43 g of a polyester polycarbonate.

The number average molecular weight (B method according to JIS K 1577) of the obtained polyester polycarbonate diol was 992, the acid value was 0.02 mgKOH/g, the weight average molecular weight was 2,800, and the degree of dispersion was 2.1. Further, the viscosity is shown in Table 1.

Example 2

The starting material was added in the form of 1,6-hexanediol: 1,5-pentanediol = 48:52 (mole ratio). Further, a raw material was added in such a manner that a total of 1,6-hexanediol and 1,5-pentanediol: ε-caprolactone = 7:3 (mole ratio).

In a 1000 ml glass round bottom flask equipped with a rectification column, a stirrer, a thermometer, and a nitrogen introduction tube, 292.8 g (3.25 mol) of dimethyl carbonate and 162.9 g (1.38 mol) of 1,6-hexanediol were added. 5-pentanediol 155.5g (1.49mol), ε-caprolactone 140.5g (1.23mol), titanium tetrabutoxide 0.05g, and distilled methanol and carbonic acid under normal pressure and stirring in a nitrogen stream The mixture of methyl esters was subjected to a transesterification reaction for 10 hours. At this time, the reaction temperature was gradually raised from 95 ° C to 200 ° C, and the composition of the distillate was adjusted to become an azeotropic composition of methanol and dimethyl carbonate, or a composition thereof.

Thereafter, the pressure was gradually reduced to 30 mmHg, and the mixture of methanol and dimethyl carbonate was distilled off while stirring, and the transesterification reaction was further carried out at 180 ° C for 10 hours. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction liquid was cooled to room temperature to obtain 501.03 g of a polyester polycarbonate.

The number average molecular weight (B method according to JIS K 1577) of the obtained polyester polycarbonate diol was 985, the acid value was 0.03 mgKOH/g, the weight average molecular weight was 2,800, and the degree of dispersion was 2.1. Further, the viscosity is shown in Table 1.

Example 3

In a 1000 ml glass round bottom flask equipped with a rectification column, a stirrer, a thermometer, and a nitrogen introduction tube, 351.8 g (3.91 mol) of dimethyl carbonate and 169.5 g (1.43 mol) of 1,6-hexanediol were added. 5-pentanediol 168.4g (1.62mol), ε-caprolactone 38.7g (0.34mol), titanium tetrabutoxide 0.05g, and distilled methanol and carbonic acid under normal pressure and stirring in a nitrogen stream The mixture of the methyl esters was subjected to a transesterification reaction for 11 hours. At this time, the reaction temperature was gradually raised from 95 ° C to 200 ° C, and the composition of the distillate was adjusted to become an azeotropic composition of methanol and dimethyl carbonate, or a composition thereof.

Thereafter, the pressure was gradually reduced to 30 mmHg, and the mixture of methanol and dimethyl carbonate was distilled off while stirring, and the transesterification reaction was further carried out at 180 ° C for 10 hours. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction liquid was cooled to room temperature to obtain 430.37 g of a polyester polycarbonate diol.

The number average molecular weight (B method according to JIS K 1577) of the obtained polyester polycarbonate diol was 1938, the acid value was 0.03 mgKOH/g, the weight average molecular weight was 5,500, and the degree of dispersion was 2.2. Further, the viscosity is shown in Table 1.

Example 4

The starting material was added in the form of 1,6-hexanediol: 1,5-pentanediol = 48:52 (mole ratio). Further, a raw material was added in such a manner that a total of 1,6-hexanediol and 1,5-pentanediol: ε-caprolactone = 97:3 (mole ratio).

In a 1000 ml glass round bottom flask equipped with a rectification column, a stirrer, a thermometer, and a nitrogen introduction tube, 377.2 g (4.19 mol) of dimethyl carbonate and 201.0 g (1.70 mol) of 1,6-hexanediol were added. 5-pentanediol 192.0 g (1.84 mol), ε-caprolactone 11.3 g (0.1 mol), titanium tetrabutoxide 0.05 g, and under normal pressure and stirring, The transesterification reaction was carried out for 10 hours while distilling off a mixture of methanol and dimethyl carbonate in a nitrogen stream. At this time, the reaction temperature was gradually raised from 95 ° C to 200 ° C, and the composition of the distillate was adjusted to become an azeotropic composition of methanol and dimethyl carbonate, or a composition thereof.

Thereafter, the pressure was gradually reduced to 30 mmHg, and the mixture of methanol and dimethyl carbonate was distilled off while stirring, and the transesterification reaction was further carried out at 180 ° C for 10 hours. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction liquid was cooled to room temperature to obtain 458.21 g of a polyester polycarbonate.

The number average molecular weight (B method according to JIS K 1577) of the obtained polyester polycarbonate diol was 993, the acid value was 0.02 mgKOH/g, the weight average molecular weight was 2,800, and the degree of dispersion was 2.1. Further, the viscosity is shown in Table 1.

Comparative example 1

In a 1000 ml glass round bottom flask equipped with a rectification column, a stirrer, a thermometer, and a nitrogen introduction tube, 372.0 g (4.13 mol) of dimethyl carbonate and 195.6 g (1.66 mol) of 1,6-hexanediol were added. 186.8 g (1.79 mol) of 5-pentanediol and 0.05 g of titanium tetrabutoxide were subjected to a transesterification reaction for 10 hours while distilling off a mixture of methanol and dimethyl carbonate under a nitrogen atmosphere with stirring. At this time, the reaction temperature was gradually raised from 95 ° C to 200 ° C, and the composition of the distillate was adjusted to become an azeotropic composition of methanol and dimethyl carbonate, or a composition thereof.

Thereafter, the pressure was gradually reduced to 30 mmHg, and the mixture of methanol and dimethyl carbonate was distilled off while stirring, and the transesterification reaction was further carried out at 180 ° C for 10 hours. After the reaction is completed (after the distillation of methanol and dimethyl carbonate is completed), the reaction solution is cooled to room temperature to obtain a polyester polycarbonate diol. 439.20g.

The number average molecular weight (B method according to JIS K 1577) of the obtained polyester polycarbonate diol was 991, the acid value was 0.05 mgKOH/g, the weight average molecular weight was 2,900, and the degree of dispersion was 2.2. Further, the viscosity is shown in Table 1.

Comparative example 2

In a 1000 ml glass round bottom flask equipped with a rectification column, a stirrer, a thermometer, and a nitrogen introduction tube, 387.0 g (4.30 mol) of dimethyl carbonate and 185.2 g (1.57 mol) of 1,6-hexanediol were added. 15-4.0 g (1.77 mol) of 5-pentanediol and 0.05 g of titanium tetrabutoxide were subjected to a transesterification reaction for 12 hours while distilling off a mixture of methanol and dimethyl carbonate under a nitrogen atmosphere with stirring. At this time, the reaction temperature was gradually raised from 95 ° C to 200 ° C, and the composition of the distillate was adjusted to become an azeotropic composition of methanol and dimethyl carbonate, or a composition thereof.

Thereafter, the pressure was gradually reduced to 30 mmHg, and the mixture of methanol and dimethyl carbonate was distilled off while stirring, and the transesterification reaction was further carried out at 180 ° C for 10 hours. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction liquid was cooled to room temperature to obtain 422.01 g of a polyester polycarbonate.

The number average molecular weight (B method according to JIS K 1577) of the obtained polycarbonate diol was 1,934, the acid value was 0.04 mgKOH/g, the weight average molecular weight was 5,600, and the degree of dispersion was 2.2. Further, the viscosity is shown in Table 1.

Application Examples 1 to 4, Comparative Application Examples 1 and 2

92.2 g of the polyester polycarbonate diol of Example 1, 41.5 g of isophorone diisocyanate (IPDI), 23.1 g of 2-hydroxyethyl acrylate (HEA), and an urethane catalyst (ZrAcAc: acetamidine) were added. 0.09 g of acetone zirconium) and 0.16 g of p-methoxyphenol (polymerization inhibitor) were reacted to obtain a urethane acrylate. The obtained urethane acrylate (UA) and 2-hydroxyethyl acrylate (HEA) were mixed in a weight ratio shown in Table 2 to obtain a composition of Application Example 1. The composition was prepared in the same manner using the polyester polycarbonate diols of Examples 2 to 4 and the polycarbonate diols of Comparative Examples 1 and 2. The viscosity of the obtained urethane acrylate (UA) and composition is shown in Table 2.

The urethane acrylate of each of the application examples and the comparative application examples and the 2-hydroxyethyl acrylate were mixed at a weight ratio of 0.8:0.2, and Irgacure 819 (manufactured by BASF Corporation) as a starter was added to 80 parts by weight of the mixture. A coating agent was obtained in parts by weight and 19 parts by weight of ethyl acetate as a solvent.

The obtained coating agent was subjected to the following measurement. The results are shown in Table 3.

Adhesiveness: The coating agent was applied to each substrate so as to have a film thickness of 0.07 mm after drying, and dried at 80 ° C for 30 minutes, and then hardened with a high-pressure mercury lamp at a cumulative light amount of 1000 mJ/cm ² and allowed to stand at room temperature for one day. Thereafter, 100 sheets of 10 × 10 were cut with a blade at a size of 4 cm ² , and a checkerboard peeling test was performed using a transparent tape. Specifically, the transparent tape is pasted, peeled, and fixed, and the number of remaining cells is counted, and the measurement results are expressed as follows.

100/10: 100 cells remained after 10 peel tests.

48 cells remained after 48/1:1 peel test.

0 grids remained after 0/1:1 peel test.

ABS: acrylonitrile-butadiene-styrene, PET: Polyethylene terephthalate

EPDM: ethylene-propylene-diene rubber, PC: Polycarbonate

As is apparent from the results of Table 3, when the polyester polycarbonate polyol of the present invention is used, a coating agent having high adhesion to EPDM can be obtained.

Further, the following measurement was carried out on the obtained coating agent. The results are shown in Table 4.

Solvent resistance: The coating agent was applied to the substrate so that the film thickness became 0.07 mm after drying, and after drying at 80 ° C for 30 minutes, a high-pressure mercury lamp was used and hardened at a cumulative light amount of 1000 mJ/cm ² , and allowed to stand at room temperature for one day. Thereafter, the absorbent cotton dipped in each solvent was placed for 24 hours, wiped with a wiping cloth, and visually evaluated.

○: The coating film is not deuterated after wiping

○-: There are traces of cotton wool or fog after wiping

△: There is a little bit of protrusion after wiping

As is clear from the results of Table 4, the coating agent obtained from the polyester polycarbonate polyol of the present invention is not only resistant to inorganic acidity, organic acid resistance, but also high in neutral lotion resistance.

Industrial availability

By using the polyester polycarbonate polyol of the present invention as a raw material of a polyurethane resin or a urethane acrylate, a coating film having excellent adhesion can be obtained, and industrial applicability is relatively high.

Claims (13)

A polyester polycarbonate polyol containing a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a hydroxyl group at a molecular terminal, wherein the following formula (1) The repeating unit shown includes two or more repeating units represented by the following formula (3) In the formula (1), R ¹ represents a divalent hydrocarbon group having 2 to 20 carbon atoms In the formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms In the formula (3), n represents an integer of 2 to 20. The polyester polycarbonate polyol according to claim 1, wherein the amount of the repeating unit represented by the formula (2) is in the total of the repeating units represented by the formulas (1) and (2). It is 1 to 60 mol%. The polyester polycarbonate polyol according to claim 1 or 2, wherein the amount of the repeating unit represented by the formula (3) is 60 to 100 in the repeating unit represented by the formula (1). ear%. The polyester polycarbonate polyol according to any one of claims 1 to 3, wherein the repeating unit represented by the formula (3) is a repeating unit represented by the formula (4) to (7) Two or more selected in the group The polyester polycarbonate polyol according to claim 4, wherein the repeating unit represented by the formula (3) is a repeating unit represented by the formula (5) and the formula (7). The polyester polycarbonate polyol according to claim 5, wherein the amount of the repeating unit represented by the formula (5) is 30 to 30 in the repeating unit represented by the formula (5) and the formula (7) 95% by mole. The polyester polycarbonate polyol according to claim 4, wherein the repeating unit represented by the formula (3) is a repeating unit represented by the formula (6) and the formula (7). The polyester polycarbonate polyol according to claim 7, wherein the amount of the repeating unit represented by the formula (6) is 20 to 20 in the repeating unit represented by the formula (6) and the formula (7) 80% by mole. The polyester polycarbonate polyol according to any one of claims 1 to 8, wherein the repeating unit represented by the formula (2) is represented by the formulas (4') to (7'). One or more selected from the group of repeating units The polyester polycarbonate polyol according to claim 9, wherein the repeating unit represented by the formula (2) is a repeating unit represented by the formula (6'). The polyester polycarbonate polyol according to any one of claims 1 to 10, wherein the number average molecular weight is from 500 to 5,000. A polyurethane resin and a polyvalent isocyanate according to any one of claims 1 to 11 Copolymerization income. A urethane acrylate which is obtained by reacting a polyester polycarbonate polyol, a polyvalent isocyanate, and a hydroxyl group-containing (meth) acrylate according to any one of claims 1 to 11.