WO2015163484A1

WO2015163484A1 - Article coated with antifogging coating having excellent durability

Info

Publication number: WO2015163484A1
Application number: PCT/JP2015/062705
Authority: WO
Inventors: 憲秀榎本; 太一小川; 大亮遠藤
Original assignee: ミドリ安全株式会社
Priority date: 2014-04-25
Filing date: 2015-04-27
Publication date: 2015-10-29
Also published as: TW201601922A; JP2015214693A

Abstract

An article coated with an antifogging coating, having an antifogging coating film for polyurethane resin compositions having an (AB) n-type multi-block copolymer basic structure comprising a diisocyanate component (A) indicated by chemical formula (1) and a branched diol component and/or a straight-chain diol component, as a diol component (B), said antifogging coating film being formed upon, as a polycyclohexylenedimethylene terephthalate copolyester resin, a poly (1, 4-cyclohexylenedimethylene terephthalate) copolyester resin base material including a terephthalic acid (TPA) or dimethyl teraphthlate (DMA) residue, a 1,4-cyclohexane dimethanol (CHDM) residue, and a 2,2-4, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residue.

Description

Anti-fogging coated article with excellent durability

The present invention relates to an antifogging coating-coated article in which an antifogging coating film is formed on a polycyclohexylenedimethylene terephthalate copolyester resin base material. In particular, the present invention relates to an antifogging coated article in which an antifogging urethane resin coating film is formed on poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin.

Polyester resin (polyester resin manufactured by Eastman Chemical Co., Ltd., called Tritan TX2001) is used as a heat-bonding resin sheet base material for resin base materials such as polycarbonate used for polarizing lens applications. It is disclosed that a cloudy coating film is formed (Patent Document 1). Disclosure of forming a film composed of a polyurethane primer layer and a silicone varnish on the same type of thermoplastic alicyclic copolyester resin substrate (trade name “Tritan” manufactured by Eastman Chemical Co., Ltd.) used for optical applications, etc. (Patent Document 2). Here, the above-mentioned copolyester resins are defined as alicyclic copolyesters obtained by polycondensation of two types of aliphatic alcohols and one type of acid.

In general, the coating of a water-soluble resin composition containing a surfactant is hydrophilic, so the initial antifogging property is good, but durability such as water wiping and dry wiping and adhesion to a resin substrate There was a problem that the sex was not enough. In addition, for example, isophorone diisocyanate or hexamethylene diisocyanate as a crosslinking agent having an isocyanate group as a crosslinking agent having an isocyanate group, which acts as a crosslinking agent in the antifogging vinyl resin composition, vinyl having a hydroxyl group forming a crosslinked structure. An antifogging vinyl resin composition containing, for example, trimethylolamine or the like as a system monomer component and a dialkylsulfosuccinate as a surfactant is disclosed (Patent Document 3). An antifogging resin coating composition containing an N-methylol group or an N-alkoxymethylol group as a crosslinking functional group of a water-soluble vinyl monomer is also disclosed (Patent Documents 4 and 5). However, there is a problem that the surfactant and the uncrosslinked copolymer are dissolved from the coating film and deposited. Moreover, the acrylic resin containing surfactant is known as an anti-fogging processing agent for a film use (patent document 6).

However, the above antifogging coating composition has a problem that antifogging durability and adhesion are not sufficient as an antifogging coating film formed on a polycyclohexylenedimethylene terephthalate copolyester resin base material. was there. In the anti-fogging resin coating composition containing a urethane resin, the urethane resin composition can form a coating film by a polycondensation reaction of an isocyanate and a polyol, but the recommended curing temperature is high, and polycyclohexylenedimethylene is used. As an antifogging coating film formed on the resin substrate by curing near the heat-resistant temperature of the terephthalate copolyester resin, there is a problem that antifogging durability and adhesion are not sufficient. Here, polycyclohexylenedimethylene terephthalate copolyester resin is a copolymer containing acid component terephthalic acid (TPA) or dimethyl terephthalate (DMA), alcohol or diol component cyclohexanedimethanol (CHDM), or cyclobutanediol (CBD). It means a polyester resin, and includes the above-mentioned polyester resin (a copolyester resin manufactured by Eastman Chemical Co., called Tritan).

JP 2012-215725 A Special table 2013-521157 gazette JP 2010-150351 A Japanese Patent Laid-Open No. 2004-250601 JP 2003-105255 A JP 2001-247632 A International Publication WO / 2012/111860 Japanese Patent Laid-Open No. 2003-026867 JP 2009-256124 A Japanese Patent Laid-Open No. 9-059603

In view of the above-mentioned problems related to the anti-fogging coating film, the present invention provides a polycyclohexylene dimethylene terephthalate copolyester resin, particularly poly (1,4-cyclohexylene dimethylene terephthalate), which is a transparent resin excellent in chemical resistance. ) An object of the present invention is to provide an antifogging coated article in which an antifogging coating film having good durability and adhesion is formed on a copolyester resin substrate. For example, poly (1,4-cyclohexylenedimethylene terephthalate) having a weather resistance formulation containing an ultraviolet absorber and a hydrolysis inhibitor disclosed in International Publication WO / 2012/111860 by the present applicant as additives. A copolyester resin is preferred.

In the present invention, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin as the base material for forming the antifogging coating film preferably has a terephthalic acid (TPA) or dimethyl terephthalate (DMA) residue. 50 mol%, 1,4-cyclohexanedimethanol (CHDM) residue 15-20 mol%, and 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue 30-35 mol% Including. The poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin is more preferably 50 mol% terephthalic acid (TPA) residue, 16 mol% 1,4-cyclohexanedimethanol (CHDM) residue, and It contains 32 mol% of 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue.

In the present invention, the diisocyanate component A and the diol component B represented by the following

chemical formulas

2 and 3 represented by the following chemical formula 1, the branched diol component (hard segment) represented by the chemical formula 4, and / or the chemical formula 5 An antifogging coating film of a polyurethane resin composition having a basic structure of an (AB) n-type multi-block copolymer composed of a linear diol component (soft segment) or a side chain diol component represented by Chemical Formula 6 Terephthalic acid (TPA) or dimethyl terephthalate (DMA) residue 50 mol%, 1,4-cyclohexanedimethanol (CHDM) residue 15 to 20 mol%, and 2,2-4,4-tetramethyl-1 Poly (1,1,3-cyclobutanediol (TMCD) residues containing 30-35 mol% - a anti-fogging resin coating coated article characterized by being formed in-cyclohexylene dimethylene terephthalate) copolyester resin substrate.

Here, as the diisocyanate component used in the antifogging agent, a known chain aliphatic polyisocyanate, for example, a polyisocyanate compound having a structure in which a urethane group (NCO group) is bonded with a linear or branched alkylene group And cyclic chain aliphatic polyisocyanates, for example, polyisocyanate compounds in which an alkylene group bonded between urethane groups (NCO groups) has a cyclic structure. Examples of chain aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, and esterified products. Is done. Cycloaliphatic polyisocyanates include cyclohexane diisocyanate (including isomers), isophorone diisocyanate, dicyclohexylmethane diisocyanate, dicyclohexylmethylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and aromatic polyisocyanates. Is exemplified (see Patent Document 8).

Here, examples of the polyol forming the antifogging film include oxyalkylene-based polyols containing an appropriate amount of water-absorbing components, such as oxyethylene / oxypropylene copolymer polyols and polyethylene glycols. Examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and the isomers thereof (see Patent Document 9).

In Formula 1, R1 is a linear or cyclic substituted or unsubstituted alkyl group and is generally represented by C _n H _2n , where n is an integer of 1 or more, preferably an integer of 1 to 10 is there. R2 is a branched substituted or unsubstituted alkoxy group and is generally represented by CH _n · (CH ₂ O) _m , where n and m are integers satisfying n + m = 4. R3 is a linear substituted or unsubstituted glycol group, generally represented by (CH ₂ CH ₂ O) _n , where n is an integer of 1 or more, preferably an integer of 1 to 10 .

According to one embodiment of the present invention, the basic structure of the polyurethane resin of (AB) n-type multi-block copolymer is, for example, 1,6-hexamethylene represented by the following chemical formula 2 and chemical formula 3 as the diisocyanate component A: A polyether-based urethane resin composition containing diisocyanate and / or isophorone diisocyanate, trimethylolethane or trimethylolpropane represented by the following chemical formula 4 as the diol component B, and / or polyethylene glycol or heptaethylene glycol represented by the chemical formula 5 1,6-hexamethylene diisocyanate and isophorone diisocyanate as a diisocyanate component A in a structural unit on a base material comprising a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin. 60 to 70 mol% of the resin composition, and a coating film of the above urethane resin composition composed of 30 to 40 mol% of trimethylolethane and polyethylene glycol as the diol component B is formed, and is 100 ° C. to less than 130 ° C., preferably 110 ° C. to It is formed as a coating film at a curing temperature of 120 ° C.

An antifogging coated article in which a coating film of the urethane resin composition is formed on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material has film characteristics such as tensile properties and dynamic viscoelasticity. It is good and the heat resistance (load deflection) temperature of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material is 100 ° C to 110 ° C. (AB) n-type multi-block copolymer is formed in a wide temperature range, and an anti-fogging coating-coated molded article having excellent durability and adhesion can be obtained.

In the formula, l, m, and n are each an integer representing a repeating unit of the structural unit — (CH ₂ —CH ₂ —O) —, and l + m + n is 10 or more and 21 or less.

The urethane resin composition includes 1,6-hexamethylene diisocyanate represented by Chemical Formula 2 and isophorone diisocyanate represented by Chemical Formula 3, which are represented by Chemical Formula 7 in the presence of cyanuric acid which is a trimer of isocyanate. It exists in the form of 1,6-hexamethylene cyanurate shown and isophorone cyanurate shown in Formula 8. Trimethylolethane represented by Chemical Formula 4 forms a urethane bond by dehydration condensation with isocyanate to the cyanurate added to cyanuric acid as a substituent R: by these isocyanate components, and dehydrogenates with polyethylene glycol represented by Chemical Formula 5. It acts as a polyol chain extender by bonding.

Polyethylene glycol, which is a linear diol component, forms the basic molecular structure of the polyether-based urethane resin schematically shown in FIG. 1, while having a hydroxyl group (not shown) at the end of the molecular chain, exhibits hydrophilicity, and will be described later. It is thought that anti-fogging properties are developed together with the surfactant.

Here, as the surfactant used in the antifogging composition, any of an anionic surfactant, a cationic surfactant and a nonionic surfactant is known. Examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, dialkyl sulfosuccinates, and sodium polyoxyethylene alkyl ether sulfates. Examples include polyoxyethylene sulfate salts. Illustrative examples of cationic surfactants include formates and acetates such as ethanolamines and triethanolamine monostearate, lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, and lauryldimethylbenzylammonium chloride. There is a quaternary ammoniaum salt. Nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, and polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol (see Patent Document 10).

According to another aspect of the present invention, the basic structure of the polyurethane resin composition of (AB) n-type multi-block copolymer is, for example, 1, 1 represented by the above-described chemical formula 2 and / or chemical formula 3 as the diisocyanate component A. Polyether urethane resin composition containing 6-hexamethylene diisocyanate and / or isophorone diisocyanate, trimethylolpropane represented by chemical formula 4 as diol component B, and heptaethylene glycol or polyoxyethylene glyceryl ether represented by chemical formula 5 or 6 On a substrate made of a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin, 42-50 mol% of isophorone diisocyanate as the diisocyanate component A in the structural unit, and the diol component B Trimethylolpropane 14 ~ 16 mol% Te, and is formed as a coating film composed of heptaethylene glycol 36 ~ 42 mol%. Coating film of the urethane resin composition comprising an adduct represented by the following chemical formula 9 of trimethylolpropane and isophorone diisocyanate as a curing agent on the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material: And is formed as a coating film at a curing temperature of 80 ° C. to less than 120 ° C., preferably 90 ° C. to less than 110 ° C.

An anti-fogging coating-coated article in which a coating film of a urethane resin composition containing the above main agent and an additive is formed on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate has tensile properties and dynamics. Since the coating properties such as viscoelasticity are good and the heat resistance (load deflection) temperature of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate is 90 ° C. to 110 ° C., the above resin group Forms (AB) n-type multiblock copolymer with heptaethylene glycol and adducts of trimethylolpropane or trimethylolpropanol and isophorone diisocyanate in an appropriate temperature range near the heat-resistant temperature of the material, durability and adhesion An anti-fogging coating-coated molded article excellent in the above can be obtained.

A diol component such as heptaethylene glycol and polyoxyethylene glyceryl ether, together with an adduct of isophorone diisocyanate and trimethylolpropane, is a polyether-based urethane resin schematically shown in FIG. 1 in the same manner as the polyethylene glycol of the first embodiment. While forming the basic molecular structure, it has a hydroxyl group at the molecular chain end of the main chain or side chain, so it is hydrophilic and can be prevented with other surfactants described later or without the addition of surfactant components. It is thought that cloudiness is developed. Polyoxyethylene glyceryl ether is considered to exhibit better antifogging properties by adding other surfactants.

In the first embodiment of the present invention, the proper curing temperature of the urethane resin composition is 100 ° C. to less than 130 ° C., and a processing temperature of 100 ° C. to less than 130 ° C., preferably 100 ° C. to 120 ° C. The coating film formed at the treatment temperature has a cross-linking density of 1.5 × 10 ⁻⁵ to 2.0 × 10 ⁻⁴ mol / cc, preferably 5.0 × 10 ⁻⁵ to 2.0 × 10 ⁻⁴ mol / cc. It is. The heat distortion temperature (HDT) showing the heat resistance of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate side is 100 ° C. to 110 ° C. at a low load (0.455 MPa). For a heat-resistant grade copolyester resin having a temperature of from ℃ to 109 ℃, even if it is maintained at an appropriate temperature range in the vicinity of the heat distortion temperature of the copolyester resin, particularly at a treatment temperature lower than the heat deformation temperature, for example, for 30 to 240 minutes. The copolyester resin base material is not distorted during the curing reaction, and the adhesion between the coating film and the resin base material is maintained. As a result, a gap or the like is generated between the copolyester resin base material and the urethane resin coating film. It is possible to prevent deterioration of the anti-fogging property and adhesion due to water.

In the second embodiment of the present invention, the proper curing temperature of the urethane resin composition is 80 ° C. to less than 120 ° C., and is a treatment temperature of 80 ° C. to less than 120 ° C., preferably 90 ° C. to less than 110 ° C. The coating film formed at the processing temperature of 1.0 × 10 ⁻⁴ to 8.0 × 10 ⁻⁴ mol / cc, preferably about 5.0 × 10 ⁻⁴ to 7.0 × 10 ⁻⁴ mol / cc. Crosslink density. The heat distortion temperature (HDT) showing the heat resistance of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate side is about 90 ° C. to 110 ° C. at low load (0.455 MPa). Even when the copolyester resin at 94 ° C. to 104 ° C. is maintained in an appropriate temperature range in the vicinity of the heat distortion temperature of the copolyester resin, particularly at a curing temperature lower than the heat deformation temperature, for example, for 30 to 240 minutes, The copolyester resin base material is not distorted during the curing reaction, and the adhesion between the coating film and the resin base material is maintained. As a result, a gap or the like is generated between the copolyester resin base material and the urethane resin coating film. It is possible to prevent water resistance and anti-fogging properties and deterioration of adhesion.

It is a figure which shows typically the basic molecular structure of polyether-type urethane resin. It is a figure which shows the 1H-NMR spectrum of the anti-fogging urethane resin composition of this invention. It is a figure which shows the 13C-NMR spectrum of the anti-fogging urethane resin composition of this invention. It is a figure which shows the dynamic viscoelasticity measurement result of the anti-fogging urethane resin coating film (120 degreeC hardening) of this invention. It is a figure which shows the dynamic viscoelasticity measurement result of the anti-fogging urethane resin coating film (130 degreeC hardening) of this invention. It is a figure which shows the dynamic viscoelasticity measurement result of the anti-fogging urethane resin coating film (100 degreeC hardening) of this invention.

The present invention is an (AB) n-type multiblock composed of a diisocyanate component A, a diol component B, a branched diol component (hard segment), and / or a linear diol component (soft segment) represented by the following chemical formula 10 An anti-fogging coating film of a polyurethane resin composition having a basic copolymer structure is used as a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin with terephthalic acid (TPA) or dimethyl terephthalate (DMA) residues. 50 mol%, 1,4-cyclohexanedimethanol (CHDM) residue 15-20 mol%, and 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue 30-35 mol% An anti-fogging coating-coated article formed on a substrate containing . The additive is preferably a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin that has been subjected to a weather resistance formulation containing an ultraviolet absorber and a hydrolysis inhibitor (see Patent Document 7).

<Base material>
The base material constituting the antifogging coating-coated article is made of poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin. Illustratively, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin comprises terephthalic acid (TPA) or dimethyl terephthalate (DMA), 1,4-cyclohexanedimethanol (CHDM), and 2,2- It is composed of 4,4-tetramethyl-1,3-cyclobutanediol (TMCD). The antifogging coating-coated product is an antifogging coating in which a coating film is formed by applying an antifogging urethane resin composition to a heat-resistant poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material. It is a coated article.

As a resin base material for forming an anti-fogging coating film, a heat-resistant poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin preferably has a terephthalic acid (TPA) or dimethyl terephthalate (DMA) residue. 50 mol%, 1,4-cyclohexanedimethanol (CHDM) residue 15-20 mol%, and 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue 30-35 mol% Including. More preferably, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin contains 50 mol% of terephthalic acid (TPA) or dimethyl terephthalate (DMA) residues and 1,4-cyclohexanedimethanol (CHDM) residues. And 16 mol% of 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue. The remainder is an ester derivative produced during the copolymerization of the copolyester resin. It may be a copolyester resin containing other polyester resin components, for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), or the like.

A poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin having the above composition comprises terephthalic acid (TPA) and 2,2-4,4-tetramethyl-1,3-cyclobutanediol compound (TMCD). The heat deformation (load deflection) temperature (HDT) showing a high esterification rate and heat resistance is 100 ° C. to 110 ° C., for example, 104 ° C. to 109 ° C. at a low load (0.455 MPa).

As a base material for forming an antifogging coating film, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin may be a copolyester resin containing a polycarbonate (PC) resin component. Illustratively, the normal grade poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin preferably contains 50 mol% terephthalic acid (TPA) or dimethyl terephthalate (DMA) residues, 1,4-cyclohexane. It contains 8-15 mol% of dimethanol (CHDM) residues and 35-42 mol% of 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues.

As a base material for forming an antifogging coating film, a normal grade poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin more preferably contains terephthalic acid (TPA) or dimethyl terephthalate (DMA) residues. 50 mol%, 10 mol% of 1,4-cyclohexanedimethanol (CHDM) residue, and 38 mol% of 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue.

In one embodiment, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin composition contains 100 parts by weight of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin with respect to the polycarbonate resin. It is contained in an amount of 10 to 30% by weight, preferably 20 to 30% by weight. When the mixing ratio of polycarbonate resin / copolyester resin is less than 10% by weight, the heat resistance is lowered. When the mixing ratio of polycarbonate resin / copolyester resin is more than 30% by weight, chemical resistance is lowered. Anti-fogging coating coated molded product is formed by coating anti-fogging urethane resin composition on copolyester resin base material containing polycarbonate resin on poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin. An anti-fogging coated article.

A copolyester resin base material containing a polycarbonate resin in a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin having the above composition has a heat deformation (load deflection) temperature (HDT) exhibiting heat resistance, for example, It is 104 ° C to 109 ° C at a low load (0.455 MPa). When the mixing ratio of polycarbonate resin / copolyester resin is less than 10% by weight, the heat resistance is lowered. When the mixing ratio of polycarbonate resin / copolyester resin is more than 30% by weight, the chemical resistance decreases (for example, see International Publication WO / 2013/065740).

<Anti-fogging urethane resin composition>
The antifogging urethane resin composition in the present embodiment is a polyurethane resin composition that forms the basic structure of the (AB) n-type multi-block copolymer, and the diisocyanate component A and the diol component B are low molecular branched diol components. (Hard segment) and / or polymer linear diol component (soft segment).

Here, the diisocyanate component A includes diisocyanate compounds having two or more isocyanate groups in one molecule, preferably at the end of the molecular chain, and derivatives thereof. The low-molecular branched diol component of the diol component B is a diol compound having two or three or more hydroxyl groups in one molecule, preferably at the end of the molecular chain, and derivatives thereof. The polymer linear diol component of the diol component B is a diol compound having two or more hydroxyl groups in one molecule, preferably at the end of the molecular chain, and derivatives thereof.

In the present embodiment, the polyurethane resin composition includes a low molecular diol component b1 represented by the chemical formula 12 and / or a polymer diol represented by the chemical formula 13 as the diisocyanate component A and the diol component B represented by the following chemical formula 11. It is a polyether-based urethane resin composition containing component b2.

In the formula, R1 is a linear or cyclic substituted or unsubstituted group. R1 is preferably a linear or cyclic substituted or unsubstituted alkyl group, generally represented by C _n H _2n , where n is an integer of 1 or more, preferably an integer of 1 to 10.

In the formula, R2 is a branched substituted or unsubstituted group. R2 is preferably a branched substituted or unsubstituted alkoxy group, generally represented by CH _n · (CH ₂ O) _m , where n and m are integers satisfying n + m = 4.

In the formula, R3 is a linear substituted or unsubstituted group. R3 is preferably a linear substituted or unsubstituted glycol group, generally represented by (CH ₂ CH ₂ O) _n , where n is an integer of 1 or more, preferably an integer of 1 to 10 .

The diisocyanate component A represented by the chemical formula 11 is crosslinked as the diol component B with the low molecular branched diol component (hard segment) represented by the chemical formula 12, and the polymer linear diol component (soft segment) represented by the chemical formula 13 In addition, the basic structure of the (AB) n-type multi-block copolymer represented by Chemical Formula 14 is constructed. (AB) The n-type multi-block copolymer has a low molecular branched diol component b1 and a high molecular linear diol component b2 as molecular structural units bonded to the isocyanate group of the diisocyanate component A represented by the chemical formula 11, Specifically, it has a crosslinked structure of the branched monomer polyol shown in FIG. The straight chain diol component (soft segment) represented by Chemical Formula 13 is not limited to a diol component in which an OH group is disposed at the end group of the main chain, but includes, for example, an OH group disposed in a partial alkyl group of the side chain. A diol component having polyoxyethylene glyceryl ether and the like.

In a preferred embodiment, the urethane resin composition is a polyether urethane resin composition having a basic structure of a polyurethane resin of (AB) n type multi-block copolymer. For example, as the diisocyanate component A represented by the chemical formula 11, 1,6-hexamethylene diisocyanate of the following chemical formula 15 and / or isophorone diisocyanate of the chemical formula 16, and as the low molecular diol component b1 of the diol component B represented by the chemical formula 12, the chemical formula 17 A polyether-based urethane resin composition containing trimethylolethane or trimethylolpropane, and / or polyethylene glycol or heptaethylene glycol of formula 18 as the polymer diol component b2 represented by formula 13. The polyether-based urethane resin composition is composed of isophorone diisocyanate represented by the chemical formula 16 as the diisocyanate component A, trimethylolpropane of the low molecular diol component represented by the chemical formula 17 as the diol component B, and / or the chemical formula 18 or the chemical formula 19. A urethane resin composition containing heptaethylene glycol or polyoxyethylene glyceryl ether of the polymer diol component shown is included.

In the film formed by coating the above urethane resin composition on a substrate, the structural unit preferably has 1,6-hexamethylene diisocyanate represented by the chemical formula 15 as the diisocyanate component A and the chemical formula 16. It is composed of 60 to 70 mol% of isophorone diisocyanate, a low molecular diol component as the diol component B, and trimethylolethane represented by the chemical formula 17 as the diol component and / or 30 to 40 mol% of the polyethylene glycol represented by the chemical formula 18. Alternatively, heptaethylene glycol represented by Chemical Formula 18 or polyoxyethylene glyceryl ether represented by Chemical Formula 19 can be included.

In one embodiment, the antifogging urethane resin composition is a one-component thermosetting resin composition, and as the diisocyanate component A, 1,6-hexamethylene diisocyanate 14 mol%, isophorone diisocyanate 52 mol%, the low molecular weight The diol component B and the polymer diol component C are composed of 21 mol% trimethylolethane and 14 mol% polyethylene glycol.

The above urethane resin composition is preferably contained as an active ingredient in the following organic solvent in an amount of 20 to 30% by weight. Suitable organic solvents are, for example, 1-methoxy-2-propanol, 2-methoxy-1-methylethyl acetate, diacetone alcohol, and toluene, and these are preferably used in combination. The solvent preferably contains 30 to 60% by weight of 1-methoxy-2-propanol, 1 to 5% by weight of 2-methoxy-1-methylethyl acetate, 10 to 30% by weight of diacetone alcohol, and 1% by weight of toluene. Less than may be included.

The above urethane resin composition contains 1,6-hexamethylene diisocyanate and / or isophorone diisocyanate as the isocyanate component represented by Chemical Formula 2 and Chemical Formula 3, and these in the presence of cyanuric acid which is a trimer of isocyanate. It exists in the form of 1,6-hexamethylene cyanurate represented by the chemical formula 20 and isophorone cyanurate represented by the chemical formula 21. Trimethylolethane, which is a low molecular branched diol component represented by Chemical Formula 4, forms a urethane bond by dehydration condensation with isocyanate, to the cyanurate added to cyanuric acid as a substituent R: these isocyanate components as a diol component. It acts as a polyol chain extender by dehydrogenation with polyethylene glycol, which is a polymer linear diol component represented by Chemical Formula 5. Polyethylene glycol, which is a polymer linear diol component, forms the basic molecular structure of the polyether-based urethane resin schematically shown in FIG. 1, while having a hydroxyl group that is a hydrophilic group at the end of the molecular chain. It is thought that anti-fogging properties are developed together with the active agent.

<Blocking agent>
The urethane resin composition may contain an aromatic hydroxyl group-containing compound such as phenols and pyrazoles as a blocking agent, and preferably contains 3,5-dimethylpyrazole. 3,5-dimethylpyrazole binds to the isocyanate components 1,6-hexamethylene diisocyanate and isophorone diisocyanate, for example, as shown in Chemical Formula 22 and Chemical Formula 23. 3,5-dimethylpyrazole prevents a polycondensation reaction with a polyol component from normal temperature to an appropriate curing temperature, and a one-component curable urethane resin composition that is stable at normal temperature can be obtained.

<Surfactant>
The urethane resin composition may contain a known nonionic surfactant, a cationic surfactant, and an anionic surfactant as a surfactant component in the composition having antifogging properties described above. For example, it contains 10 to 20% by weight as a dialkyl sulfonate which is an anionic surfactant. Preferably, sodium di (2-ethylhexyl) sulfosuccinate represented by the chemical formula 24 is preferably contained in the above organic solvent as an active ingredient in an amount of 5 to 10% by weight. Sodium di (2-ethylhexyl) sulfosuccinate acts as a stabilizer in an organic solvent and exhibits antifogging properties as a hydrophilic compound having a sulfonic acid group and a carboxyl group in a coating film of a urethane resin composition. It is an active ingredient to do.

In another embodiment, the antifogging urethane resin composition is a two-component thermosetting resin composition, the diisocyanate component A being 42 to 50 mol% of isophorone diisocyanate represented by the chemical formula 16, and the diol component B being the chemical formula 17 Is a thermosetting resin composition composed of 14 to 16 mol% of trimethylolpropane represented by formula (36) and 36 to 42 mol% of heptaethylene glycol represented by the chemical formula (18). The two-component thermosetting resin composition has a chemical formula as a substitute for isophorone diisocyanate represented by chemical formula 16 as the diisocyanate component A, trimethylolpropane represented by chemical formula 17 as the diol component B, and heptaethylene glycol represented by chemical formula 18. The thermosetting resin composition containing the polyoxyethylene glyceryl ether shown by 19 may be sufficient. Note that sodium di (2-ethylhexyl) sulfosuccinate represented by the chemical formula 24 exhibits antifogging properties even in a two-component thermosetting resin composition containing polyoxyethylene glyceryl ether represented by the following chemical formula 25. It is considered to be an active ingredient for In this case, sodium di (2-ethylhexyl) sulfosuccinate represented by the above chemical formula 24 is preferably contained in an organic solvent as an active ingredient at about 4.7% by weight.

In the formula, l, m, and n are each an integer of 1 or more, and l + m + n is 10 or more and 21 or less, and l + m ≧ n.

The urethane resin composition is preferably contained in an amount of 20 to 50% by weight as an active ingredient in the following organic solvent. Suitable organic solvents include, for example, dodecanol, NN-bis (N-decyl) methylamine, diacetone alcohol, and ethyl acetate, and these are preferably used in combination. The solvent for the main agent heptaethylene glycol preferably contains diacetone alcohol, a small amount of dodecanol, NN-bis (N-decyl) methylamine or N-methylundecylnonylamine, and isophorone diisocyanate and trimethylolpropane as curing agents. The adduct solvent may contain ethyl acetate. When heptaethylene glycol or polyoxyethylene glyceryl ether is used as the polymer diol component, the solvent preferably contains about 20 wt% of MIBK.

<Anti-fogging coating film>
After forming the above urethane-based urethane resin composition on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material by a conventional method such as coating, spraying, dipping, etc., A poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin is heat-cured at a temperature not exceeding the heat resistance temperature to form an antifogging coating film.

The anti-fogging resin-coated article of Reference Example 1 has a polyether-based urethane resin composition coating film (FSI Coating Technologies, Visgard Premium Plus) described in the above embodiment as a polycarbonate (PC) resin substrate. This is a prototype product (product name GEN2 manufactured by ASWAN) used for the formed spectacles.

The antifogging resin-coated article of Reference Example 2 is a commercial product (ASWAN, manufactured by forming a polyether-modified silicone resin coating film (SDC Technologies Asia, Crystal Coat C-380) on a polycarbonate (PC) resin substrate. ) And used for eyeglasses.

The anti-fogging resin-coated article of Reference Example 3 is a commercial product (Uvex, product name Ultravision) in which a cellulose acetate-based resin coating film (4C acetate) is formed on a polycarbonate (PC) resin base material. It is what is used.

The anti-fogging resin-coated article of Reference Example 4 is a commercial product (manufactured by Yamamoto Optical Co., Ltd., product name Petroid AF) in which a polyether-modified silicone resin coating film is formed on a polycarbonate (PC) resin substrate, and is used for eyeglass applications. Is.

The anti-fogging resin-coated article of Reference Example 5 is a commercial product (manufactured by Riken Optec Co., Ltd.) in which a polyether-based urethane resin coating film (VF coating) is formed on a polycarbonate (PC) resin substrate, and is used for eyeglass applications. Is.

Table 1 shows the results of the antifogging performance test, pencil hardness test, adhesion test, film thickness measurement, and contact angle measurement for the antifogging resin coated articles of Reference Examples 1 to 5.

In Reference Example 1 in which the polyether-based urethane resin coating film is formed, both the antifogging performance and adhesion are good, and in Reference Example 2 and Reference Example 4 in which the polyether-modified silicone resin coating film is formed, the anti-fogging performance of washing durability As for the property, it was found that the effect was lost and the antifogging performance was inferior with a very small number of repetitions. In Reference Example 3 in which the cellulose acetate-based resin coating film was formed, although the durability performance was good, it was clouded in about 20 seconds over the steam, so there was a problem in the initial antifogging performance.

Reference Example 5 is an article on which a commercially available polyether-based urethane resin coating film is formed, which has excellent anti-fogging performance and good adhesion by a cross-cut method. It was concluded that there was a gap between the material and the coating, and adhesion was not sufficient.

It was found that the polyether-based urethane resin coating composition used in Reference Example 1 was most suitable as a coating film for obtaining antifogging performance as compared with Reference Examples 2-5.

[Evaluation of anti-fogging coating film]

<Anti-fogging test>
1. Initial performance A 60 ° C vapor is applied to the sample and the number of seconds until cloudiness is measured. The determination of cloudiness is considered to be cloudy when poor visibility (including water droplets and a nonuniform water film) occurs.
2. Water Wash Test After the above antifogging test, the sample is exposed to running water for 10 seconds. The flow rate is 0.5 dm ³ / sec. After washing, place in a desiccator for 10 minutes or more, dry completely, and perform the anti-fogging test again. This operation is repeated, and the number of repetitions when the antifogging performance deteriorates from the initial performance is taken as the test result.
3. Dry wiping test After the above anti-fogging test, the sample is dried in a desiccator for 10 minutes or more. Wipe dry sample once with Kim towel. At this time, the load applied to the sample is adjusted to be 3.0 ± 0.5 kgf. The anti-fogging test is performed again on the dry-wiped sample, and the number of repetitions when the anti-fogging performance deteriorates from the initial performance is taken as the test result.

<Pencil hardness> “General paint test method-Part 5: Mechanical properties of paint film-Section 4: Scratch hardness (pencil method) (JIS K5600-5-4: 1999)”
The wick is removed by removing the xylem so that the pencil core becomes a smooth cylindrical shape without scratches. While holding the pencil vertical, place the lead against the abrasive paper and move it back and forth to flatten the tip of the lead. The tip of the pencil is applied to the sample plate, a distance of 7 mm is pressed at a speed of 0.5 mm / sec, and the coating film is examined for indentation with the naked eye. The test is performed twice, and the test result is the hardness of the hardest pencil that did not cause any scratches.

<Adhesiveness> “General test methods for paints-Part 5: Mechanical properties of coating films-Section 6: Adhesion (cross-cut method) (JIS K5600-5-6: 1999)”
1. Cross cut test Cut from the coating surface until it penetrates the substrate. The incisions are made 6 times at intervals of 2 mm, and then the incisions are repeated at 90 ° to repeat the process so that a grid pattern of 25 squares is formed. Place the adhesive tape on the lattice and attach it properly to the coating. Peel off the tape and record the number of squares where the coating is not removed.

2. Cross-sectional observation A sample is frozen and fractured, and a cross-section is observed with a SEM (scanning electron microscope) at a magnification of 200 to 1000. Whether the adhesion is good or not is determined based on whether or not there is a gap between the substrate and the coating film.

<Contact angle measurement> “Test method for wettability of substrate glass surface (JIS R3257: 1999 Test method for wettability of substrate glass surface)”
A water droplet of 1.0 μL is dropped on a horizontally placed sample, and the contact angle of the water droplet in contact with the sample is obtained by the θ / 2 method.

<Film thickness measurement>
By observation with an optical microscope, the measured value of the film thickness was obtained by converting the magnification from the actual size of the coating film formed on the resin substrate in one or more regions as the target visual field.

<Chemical resistance test>
Immerse the chemical in a 1 cm square cloth and place it on the sample and leave it for 24 hours. After removing the waste cloth and wiping with water, wipe off the moisture and observe the appearance change.

Examples of the present invention will be described. However, the present invention is not limited to the following examples.

In the first embodiment, the heat distortion temperature (HDT) indicating the heat resistance on the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate side is 100 ° C. at a low load (0.455 MPa). With respect to a heat-resistant grade copolyester resin (product name: Tritan TX2000, TX2001, manufactured by Eastman Chemical Co., Ltd.) at 110 ° C., specifically 104 ° C. to 109 ° C., in one embodiment, the urethane resin composition is properly cured. The temperature is 100 ° C. to less than 130 ° C. and is cured at a treatment temperature of 100 ° C. to less than 130 ° C., preferably 110 ° C. to 120 ° C. Even if the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin is maintained near the heat distortion temperature, particularly at a curing temperature lower than the heat distortion temperature, for example, for 30 to 240 minutes, the copolyester resin group The adhesion between the coating film and the resin substrate is maintained without distortion of the material.

The anti-fogging coated article in which the coating film of the urethane resin composition of the first embodiment is formed on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate has tensile properties and dynamics. Coating properties such as viscoelasticity are good, and (AB) n-type multi-block copolymer is formed in an appropriate temperature range near the heat-resistant temperature of the above resin base material, and has excellent durability and adhesion. A cloudy coating-coated molded product is obtained.

In the second embodiment, the heat distortion temperature (HDT) showing the heat resistance on the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate side is about 90 at low load (0.455 MPa). With respect to a copolyester resin (manufactured by Eastman Chemical Co., for example, product names TX1000 and TX1001) having a temperature of from 110 ° C. to 110 ° C., specifically from 94 ° C. to 104 ° C., an appropriate curing temperature of the urethane resin composition of one embodiment is Curing is carried out at a processing temperature of 80 ° C. to less than 120 ° C., preferably 80 ° C. to less than 120 ° C., preferably 90 ° C. to less than 110 ° C. Even if the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin is maintained at a curing temperature near the heat deformation temperature and less than the heat deformation temperature, for example, for 30 to 240 minutes, the copolyester resin base material during the curing reaction The adhesion between the coating film and the resin substrate is maintained without distortion.

An antifogging coated article in which the coating film of the urethane resin composition of the second embodiment is formed on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material has tensile properties and dynamics. Film properties such as mechanical viscoelasticity are good, and an (AB) n-type multi-block copolymer is formed in an appropriate temperature range near the heat-resistant temperature of the above resin base material, and has excellent durability and adhesion. An antifogging coating-coated molded product is obtained.

The urethane resin composition used for the antifogging resin coated article of Example 1 is a one-component thermosetting polyether-based urethane resin composition containing 27.8% by weight of a urethane resin component as an active ingredient in the following solvent. is there.

The urethane resin composition of Example 1 contains 30% by weight of 1-methoxy-2-propanol, 5% by weight of 2-methoxy-1-methylethyl acetate, 30% by weight of diacetone alcohol, and less than 1% by weight of toluene. In the solvent, the isocyanate component contains 14 mol% of 1,6-hexamethylene diisocyanate and 52 mol% of isophorone diisocyanate, which are present in the form of cyanurate. It contains 21 mol% trimethylolethane as the low molecular diol component and 14 mol% polyethylene glycol as the high molecular diol component. Further, 6.2% by weight of sodium di (2-ethylhexyl) sulfosuccinate as a surfactant component that also acts as an emulsion stabilizer can be uniformly mixed at room temperature to obtain a thermosetting urethane resin composition solution.

FIG. 2 shows the result of ¹ H-NMR measurement of the resin component precipitated in hexane of the urethane resin composition. Similarly, FIG. 3 shows the results of ¹³ C-NMR measurement of resin components precipitated in hexane.

Trimethylolethane, which is a low molecular diol component, forms a urethane bond by dehydration condensation with isocyanate, and acts as a polyol chain extender by dehydrogenation with polyethylene glycol, which is a high molecular diol component. Polyethylene glycol, which is a polymer diol component, forms the basic skeleton of a polyether-based urethane resin, while the hydroxyl group of the diol is a hydrophilic group, so that it is formed on a substrate together with the surfactant sodium di (2-ethylhexyl) sulfosuccinate. It is considered that the formed coating film exhibits antifogging properties.

The anti-fogging resin-coated article of Example 1 is obtained by applying the above one-component thermosetting urethane resin composition to a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material used for spectacles. The isocyanate component and the polyol component in the urethane resin composition are reacted by being applied by spin coating and holding for about 240 minutes at a processing temperature (110 ° C.) that does not substantially exceed the heat resistant temperature of the copolyester resin substrate. It was cured to form a urethane resin coating film. Here, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin contains 50 mol% of terephthalic acid (TPA) residues, 16 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, and 2 , 2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue is contained at 32 mol%. The remainder is a derivative produced during esterification of the terephthalic acid and the diol compound.

The anti-fogging resin-coated article of Example 2 was obtained by similarly applying the above urethane resin composition to a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material used for spectacles by spin coating. The urethane resin is cured by reacting and curing the isocyanate component and the polyol component in the urethane resin composition by applying and holding at a processing temperature (115 ° C.) that does not substantially exceed the heat resistance temperature of the copolyester resin substrate for about 180 minutes. A coating film was formed. Here, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin has the same composition as that used in Example 1.

The anti-fogging resin-coated article of Example 3 is obtained by applying the above two-component thermosetting urethane resin composition to a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material used for spectacles. The isocyanate component and the polyol component in the urethane resin composition are reacted by being applied by spin coating and holding for about 60 minutes at a processing temperature (90 ° C.) that does not substantially exceed the heat resistant temperature of the copolyester resin substrate. It was cured to form a urethane resin coating film. Here, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin has the same composition as that used in Example 1.

The antifogging resin-coated article of Comparative Example 1 is the same as the one-component thermosetting urethane resin composition described above on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material used for spectacles. Was applied by spin coating and kept at 100 ° C. for about 120 minutes, whereby the isocyanate component and the polyol component in the urethane resin composition were reacted and cured to form a urethane resin film. However, since the curing reaction was insufficient, uncured components remained in the coating, and the antifogging property was not sufficiently exhibited, and a phenomenon that the coating became sticky was observed. Here, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin has the same composition as that used in Example 1.

The anti-fogging resin-coated article of Comparative Example 2 is a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material used for spectacles, and the two-component thermosetting urethane resin composition described above. It was applied by a spin coating method and kept at 100 ° C. for about 60 minutes to be cured by reaction to form a urethane resin film. Although the adhesion and adhesion of the coating properties were sufficient, the expression of antifogging properties was not sufficient. Here, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin has the same composition as that used in Example 1.

The anti-fogging resin-coated article of Example 4 was obtained by applying the above one-component thermosetting urethane resin composition to a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material used for spectacles. The isocyanate component and the polyol component in the urethane resin composition are reacted by being applied by spin coating and holding for about 240 minutes at a processing temperature (110 ° C.) that does not substantially exceed the heat resistant temperature of the copolyester resin substrate. It was cured to form a urethane resin coating film. As a weather resistance prescription, 100 parts by weight of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin used in Example 1 was treated with an ultraviolet absorber (CYASORB UV-3638F) (0.25-1. 0) wt%, and 0.13 to 0.50 wt% of hydrolysis inhibitor (carbodilite LA-1).

The anti-fogging resin-coated article of Example 5 is the same as the one-component thermosetting urethane resin composition described above on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material used for spectacles. The isocyanate component and the polyol component in the urethane resin composition are reacted by being applied by spin coating and holding for about 240 minutes at a processing temperature (110 ° C.) that does not substantially exceed the heat resistant temperature of the copolyester resin substrate. It was cured to form a urethane resin coating film. The copolyester resin base material contains 20% by weight of a polycarbonate resin with respect to 100 parts by weight of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin used in Example 1. The anti-fogging resin-coated article of Example 6 is a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material, the above two-component thermosetting urethane resin composition, A urethane resin composition containing polyoxyethylene glyceryl ether as a substitute and MIBK as a solvent was similarly applied by dipping, and at a processing temperature (90 ° C.) substantially not exceeding the heat resistance temperature of the copolyester resin substrate. By holding for about 60 minutes, the isocyanate component and the polyol component in the urethane resin composition were reacted and cured to form a urethane resin coating film. In Example 6, the adhesion and adhesion of the antifogging resin coating film were sufficient, and the expression of antifogging properties was also sufficient. That is, the two-component thermosetting urethane resin composition of Example 6 is a normal grade poly (1,4-cyclohexylenedimethylene terephthalate) copolyester having a lower heat resistant temperature than the copolyester resin base material used in Example 1. It can also be applied to resin substrates. The antifogging resin-coated articles of Example 7 and Example 8 are the above-described two-component thermosetting urethane resin composition on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material, A urethane resin composition using polyoxyethylene glyceryl ether as a substitute of heptaethylene glycol was applied by dipping and held at 90 ° C. for about 60 minutes to be cured by reaction to form a urethane resin film. In Examples 7 and 8, the adhesion and adhesion of the coating properties were sufficient under normal conditions, and the antifogging property was also sufficiently exhibited. However, as compared with Example 6, the adhesiveness was peeled off by several squares at a high tape peeling speed. Here, the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin of Example 7 is a normal grade copolyester resin substrate and the poly (1,4-cyclohexylenedimethylene terephthalate) of Example 8. ) The copolyester resin is the heat-resistant grade copolyester resin substrate used in Example 1.

The antifogging resin coating compositions of Examples 1 and 2 and Examples 3 to 5 and the antifogging resin coating compositions of Comparative Examples 1 and 2 were prepared by being injected into a fluororesin mold coated with a release agent. The coated film was subjected to a tensile test and a dynamic viscoelasticity test. The results are shown in Table 2. Table 2-1 shows the test results for the test pieces obtained under the conditions for forming the antifogging resin coating film of Examples 1 and 2 and Comparative Example 1 as the characteristics of the antifogging resin coating film. The test results of antifogging property, adhesion, tensile test, and dynamic viscoelasticity of these antifogging resin coating films are shown. Table 2-2 shows the test results of the test pieces obtained under the film forming conditions of the antifogging resin coating films of Examples 3 to 5 and Comparative Example 2, and the antifogging properties of these antifogging resin coating films. The test results of haze, adhesion, tensile test, and dynamic viscoelasticity are shown. Table 2-3 shows the antifogging and adhesive properties of these antifogging resin coating films obtained under the coating forming conditions of the antifogging resin coating films of Example 6, Example 7, and Example 8. The test results are shown.

<Tensile test>"Plastics-Test methods for tensile properties-Part 3: Test methods for films and sheets (JIS K7127: 1999)"
A dumbbell type 5 (JISK7127) sample is prepared. A dumbbell piece is attached to the gripping tool of a tensile tester, pulled at a pulling speed of 100 mm / min, and the stress and strain at break are recorded. The average value of N = 5 is taken as the measurement result.

<Dynamic viscoelasticity test>
In FIG. 4, the dynamic viscoelasticity measurement result of the urethane resin coating film hardened | cured at the process temperature corresponding to the hardening temperature of Example 1 is shown. In FIG. 5, the dynamic viscoelasticity measurement result of the urethane resin coating film hardened | cured at the process temperature corresponding to the hardening temperature of Example 2 is shown. In FIG. 6, the dynamic viscoelasticity measurement result of the urethane resin coating film hardened | cured at the process temperature corresponding to the hardening temperature of the comparative example 1 is shown.

<Storage elastic modulus E '>
The measurement mode was tensile, the temperature rising rate was 3 ° C./min, the frequency was 10 Hz, the measurement interval was 1 ° C., and the measurement was performed from −50 ° C. to 100 ° C. in a nitrogen atmosphere. As the storage elastic modulus E ′, a value at 85 ° C. was adopted as the storage elastic modulus of the flat portion.

<Crosslink density>
Of the flat region (rubbery region) of the storage elastic modulus-temperature curve, the crosslinking density of the coating film was determined from the storage elastic modulus at 85 ° C. The calculation formula is as the following formula (1).

n: Crosslink density (mol / cc)
E ′: storage elastic modulus (dyn / cm ² )
R: Gas constant (8.31 × 10 ⁷ dyn · cm / K · mol)
T: Absolute temperature (K)

<Glass transition temperature Tg>
The glass transition temperature Tg was determined from the shoulder of the storage elastic modulus E ′ and the peak temperature of the loss tangent (tan δ).

The urethane resin coating film cured at the treatment temperature (100 ° C.) of Comparative Example 1 was not sufficiently cured because the curing temperature was low, and an uncured part remained, and a tensile test piece could not be prepared. . Comparing the tensile properties of the film cured at the treatment temperature (110 ° C.) of Example 1 and the tensile properties of the film cured at the treatment temperature (115 ° C.) of Example 2, the coating cured at the high temperature side is hard and has an elongation. There is a tendency to decrease. Furthermore, the results show that the antifogging property is lowered even if the treatment temperature is too high. Therefore, the proper curing temperature for the urethane resin coating films of Example 1 and Example 2 is 100 ° C., which does not substantially exceed the heat resistance temperature of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin substrate. To a processing temperature of 110 ° C. to less than 130 ° C., more preferably 110 ° C. to 120 ° C. However, as the heat resistance temperature of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material, the heat distortion temperature (HDT) is the temperature at which a specified amount of deflection is measured under a certain load (load deflection). Temperature) (see, for example, ASTM D648).

Compare the crosslink density of the film cured at the treatment temperature (100 ° C.) of Comparative Example 1 and leaving an uncured part, and the film sufficiently cured at the treatment temperature of Examples 1 and 2 (110 ° C. to 115 ° C.). Then, when the crosslink density of Comparative Example 1 is 1.23 × 10 ⁻⁵ mol / cc or less, curing is not sufficient, and when the crosslink density of Example 2 is 1.74 × 10 ⁻⁴ mol / cc or more, the heat of one liquid In the curing system, the curing reaction proceeds excessively, and the coating tends to be hard. The optimum crosslink density of the antifogging coating film is (1.5 × 10 ⁻⁵ to 2.0 × 10 ⁻⁴ mol / cc), preferably (5.0 × 10 ⁻⁵ to 2.0 × 10 ^{− 4} mol / cc) is estimated. On the other hand, regarding the two-component thermosetting urethane resin coating film, when Example 3 and Comparative Example 2 are compared, the curing temperature of Comparative Example 2 is as high as 100 ° C., and the crosslinking density is 7.91 × 10 ⁻⁴ mol / cc. The tensile elongation is small, and the expression of antifogging properties is insufficient. Considering that the curing temperature of Example 3 is 90 ° C. and the crosslinking density of the coating film is 5.15 × 10 ⁻⁴ mol / cc, the optimum crosslinking density of the antifogging coating film is (1. 0 × 10 ⁻⁴ to 8.0 × 10 ⁻⁴ mol / cc), preferably (5.0 × 10 ⁻⁴ to 7.0 × 10 ⁻⁴ mol / cc). One component heat using a resin substrate obtained by blending the poly (1,4-cyclohexylene dimethylene terephthalate) copolyester resin and the polycarbonate resin of Example 4 with the weather resistance formulation added to Example 1 and Example 1 In Example 5 in which a cured urethane resin coating film was formed, the curing temperature was 110 ° C., and sufficient adhesion, adhesion, and antifogging properties were exhibited. The crosslink density of the antifogging coating film was 9 .86 × 10 ⁻⁵ mol / cc but considered to be within the proper range.

Table 3 shows the results of measuring the urethane / polyol infrared absorbance ratio of the antifogging resin coating films of Examples 1 and 2 and the antifogging resin coating film of Comparative Example 1. Table 3 shows the urethane / polyol infrared absorbance ratio of the antifogging urethane resin coating film containing heptaethylene glycol as the main agent and trimethylolpropane and isophorone diisocyanate adduct as the curing agent as Example 3 and Comparative Example 2. As a measurement result, as Comparative Example 3, the measurement result of the antifogging urethane resin coating film of Reference Example 5 is shown. From these measurement results, it is estimated that the optimum range of the urethane / polyol infrared absorbance ratio of the antifogging coating film is 1.0 to 2.5.

<Urethane / polyol infrared absorbance ratio>
Fourier transform infrared spectrophotometry (FT-IR) absorbance attributable to the absorbance Abs (1530 cm ^-1) and C = O belonging to N-C-H urethane groups in the coating film by Abs (1700cm ^-1), and a polyol Absorbance Abs (1100 cm ⁻¹ ) attributed to the group was measured. It was determined urethane / polyol infrared absorbance absorbance ratio attributed to urethane and polyol groups as ratio ^{Abs (1700cm -1) / Abs (} 1100cm -1).

<N content>
Intensity correction is performed by elemental analysis of C, N, O, S, and Na based on X-ray excitation energy dispersive spectroscopy (EDX), and the N content (mass concentration) in the coating film is measured.

The absorption peak intensity ratio of urethane and polyol in FT-IR of the antifogging resin coating film of Example 1 is about 1.24, and the N content is about 8.6% by mass. For, the absorption peak intensity ratio of urethane and polyol is about 1.20, and the curing reaction proceeds sufficiently at a curing temperature of 115 ° C., so that the N content is about the same as in Example 1. Presumed. The FT-IR urethane / polyol ratio of the antifogging resin coating film of Example 3 was about 1.09, and the N content was about 7.4% by mass. As a point that the antifogging resin coating film of Examples 1 to 3 is excellent, when compared with the urethane / polyol ratio of Comparative Examples 1 and 2, it is higher than the value of 0.94 of the uncured product of Comparative Example 1, The urethane / polyol ratio which is lower than the value 2.75 of the hard coat film of Comparative Example 2 and is considered to correspond to the above range of crosslink density is within an appropriate range.

Industrial application fields

Anti-fogging coated articles in which an anti-fogging urethane resin coating film is formed on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base with excellent chemical resistance include, for example, protective glasses and face protection surfaces It can be used for such applications.

Claims

A polyurethane resin composition having the basic structure of an (AB) n-type multi-block copolymer represented by the following chemical formula 1 and comprising a diisocyanate component A, a branched diol component as the diol component B, and / or a linear diol component The anti-fogging coating film is composed of 50 mol% of terephthalic acid (TPA) or dimethyl terephthalate (DMA) residue, 15 to 20 mol% of 1,4-cyclohexanedimethanol (CHDM) residue, and 2,2-4. , 4-Tetramethyl-1,3-cyclobutanediol (TMCD) residues formed on a poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin base material containing 30 to 35 mol% Resin-coated articles.

In the formula, R1 is a linear or cyclic substituent or an unsubstituted group, R2 is a branched substituent or an unsubstituted group, and R3 is a linear substituent or an unsubstituted group.
In the antifogging coated article according to claim 1, 1,6-hexamethylene diisocyanate and / or isophorone diisocyanate represented by the following chemical formulas 2 and 3 as the diisocyanate component A, and a branched diol component as the diol component B: A polyether-based urethane resin composition containing trimethylolethane or trimethylolpropane represented by the chemical formula 4 and / or polyethylene glycol or heptaethylene glycol represented by the chemical formula 5 of the linear diol component is converted into poly (1,4- 1,6-hexamethylene diisocyanate and isophorone diisocyanate 60 to 70 mol% as the diisocyanate component A in a structural unit on a base material made of (cyclohexylene dimethylene terephthalate) copolyester resin Anti-fogging resin coating coated article characterized by being formed as a coating film composed of trimethylol ethane and polyethylene glycol 30 ~ 40 mol% as the diol component B.
Poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resins are terephthalic acid (TPA) or dimethyl terephthalate (DMA), 1,4-cyclohexanedimethanol (CHDM) and 2,2-4,4-tetra It is composed of a copolyester resin containing methyl-1,3-cyclobutanediol (TMCD), and the heat resistance temperature of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin is 100 ° C. to 110 ° C. The antifogging resin-coated article according to claim 2.
The poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin has a terephthalic acid (TPA) residue of 50 mol%, 1,4-cyclohexanedimethanol (CHDM) residue of 15 to 20 mol%, and 2 The anti-fogging resin-coated article according to claim 2, comprising 30 to 35 mol% of 1,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue.
50 mol% of terephthalic acid (TPA) residue, 8-15 mol% of 1,4-cyclohexanedimethanol (CHDM) residue, and 2,2-4,4-tetramethyl-1,3-cyclobutanediol (TMCD ) A residue of 35 to 42 mol% of poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin and 20 to 30 parts by weight of a polycarbonate resin with respect to 100 parts by weight of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin. An anti-fogging resin coating-coated article, wherein the polyether urethane resin composition according to claim 2 is formed as a coating film on a base material made of (silylene methylene terephthalate) copolyester resin.
An ultraviolet absorber is 0.25 to 1.0% by weight and a hydrolysis inhibitor is 0.13 to 0.50% by weight based on 100 parts by weight of the poly (1,4-cyclohexylenedimethylene terephthalate) copolyester resin. The anti-fogging resin-coated article according to any one of claims 2 to 5, wherein the anti-fogging resin-coated article is contained.
Claim 2, wherein the storage modulus of the coating film based on dynamic viscoelasticity test (85 ° C.) is 5.0 × 10 6 dyn / cm 2 ~ 2.0 × 10 7 dyn / cm 2 An antifogging resin-coated article as described in 1.
3. The crosslink density calculated from the following formula (1) based on a dynamic viscoelasticity test is 5.0 × 10 −5 mol / cc to 2.0 × 10 −4 mol / cc. An antifogging resin-coated article as described in 1.

n: Crosslink density (mol / cc)
E ′: storage elastic modulus (dyn / cm 2 )
R: Gas constant (8.31 × 10 7 dyn · cm / K · mol)
T: Absolute temperature (K)
The anti-corrosive agent according to claim 2, wherein the polyether-based urethane resin composition contains 5 to 10% by weight of sodium di (2-ethylhexyl) sulfosuccinate represented by the following chemical formula 6 as a surfactant. Fogging resin coating coated article.
Absorbance ratio of the Fourier transform infrared spectrophotometry (FT-IR) absorbance attributable to the absorbance Abs (1700 cm -1) and a polyol group attributed to urethane groups in the coating film by Abs (1100cm -1) Abs (1700cm -1) / The antifogging resin-coated article according to claim 2, wherein Abs (1100 cm -1 ) is 1.0 to 2.5.
The antifogging coated article according to claim 1, wherein the diisocyanate component A is isophorone diisocyanate represented by the chemical formula 3, the diol component B is the triglycolethane or trimethylolpropane represented by the chemical formula 4 of the branched diol component, and / or Alternatively, a polyether-based urethane resin composition containing heptaethylene glycol represented by Chemical Formula 5 of the linear diol component or polyoxyethylene glyceryl ether represented by Chemical Formula 7 is converted into poly (1,4-cyclohexylenedimethylene terephthalate) copolymer. On a base material made of a polyester resin, in the structural unit, isophorone diisocyanate as the diisocyanate component A, trimethylolpropane as the diol component B, and heptaethylene glycol or polyol. Anti-fogging resin coating coated article, characterized in that the shea ethylene glyceryl ether was formed as a coating film formed.

In the formula, l, m, and n are each an integer of 1 or more, and l + m + n is 10 or more and 21 or less, and l + m ≧ n.