WO2017164002A1 - ウレタン樹脂組成物、コーティング剤及び物品 - Google Patents
ウレタン樹脂組成物、コーティング剤及び物品 Download PDFInfo
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- WO2017164002A1 WO2017164002A1 PCT/JP2017/010131 JP2017010131W WO2017164002A1 WO 2017164002 A1 WO2017164002 A1 WO 2017164002A1 JP 2017010131 W JP2017010131 W JP 2017010131W WO 2017164002 A1 WO2017164002 A1 WO 2017164002A1
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- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/40—High-molecular-weight compounds
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a urethane resin composition that can be used in various applications such as a coating agent and an adhesive.
- Urethane resin compositions are generally used in various applications including coating agents and adhesives because they have good adhesion to substrates and can form flexible coatings.
- the urethane resin composition may be, for example, an aqueous polyurethane dispersion, a) at least one organic aliphatic, alicyclic or aromatic di, tri or polyisocyanate, b) at least one isocyanate reactive.
- the coating film formed using the aqueous polyurethane dispersion is stretched or bent. Since it is not sufficient in terms of flexibility such as property, whitening or the like may be caused when the coated object is bent. Further, since the coating film formed using the aqueous polyurethane dispersion is not sufficient in terms of hardness, for example, when used for a surface coating agent such as a touch panel, the coating film is easily damaged and may cause poor appearance.
- the problem to be solved by the present invention is to provide a urethane resin composition capable of forming a coating film having excellent hardness, scratch resistance and flexibility.
- a1- 1 alkylene diol having a carbon number of 1 to 9 having two or more polymerizable unsaturated groups
- urethane resin (A) using oxyalkylenediol (a1-2) having 1 to 5 carbon atoms having two or more polymerizable unsaturated groups, and urethane resin containing polyfunctional acrylate (B)
- the inventors have found that the above problems can be solved by using the composition, and have completed the present invention.
- the present invention relates to an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two or more polymerizable groups represented by the following general formula (2).
- Urethane resin (A) which is a reaction product of polyol (a1) containing oxyalkylenediol (a1-2) having a saturated group and polyisocyanate (a2), polyfunctional acrylate (B), and solvent (C In the range of 2.5 to 9.5 mmol / g of the polymerizable unsaturated bond in the total of the urethane resin (A) and the polyfunctional acrylate (B).
- the present invention relates to a urethane resin composition.
- R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
- R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
- R 2 represents an alkylene group having 1 to 5 carbon atoms. .
- the urethane resin composition of the present invention can form a coating film having excellent hardness, scratch resistance and flexibility, for example, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / It can be suitably used as a coating agent and adhesive for plastic substrates such as PC resin, polystyrene resin (PS resin), polymethacrylic acid resin (PMMA resin), and polyester resin (PET resin).
- ABS resin acrylonitrile-butadiene-styrene resin
- PS resin polystyrene resin
- PMMA resin polymethacrylic acid resin
- PET resin polyester resin
- the urethane resin composition of the present invention comprises an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two or more represented by the following general formula (2).
- a urethane resin (A) which is a reaction product of a polyol (a1) containing an oxyalkylenediol (a1-2) having a polymerizable unsaturated group and a polyisocyanate (a2), a polyfunctional acrylate (B), and It is characterized by containing a solvent (C).
- urethane resin (A) among the urethane resins having a polymerizable unsaturated group, an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or the following A reaction product of a polyol (a1) containing an oxyalkylenediol (a1-2) having two or more polymerizable unsaturated groups represented by the general formula (2) and a polyisocyanate (a2) is used.
- R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
- R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
- R 2 represents an alkylene group having 1 to 5 carbon atoms. .
- polyol (a1) used for the production of the urethane resin (A) two or more polymerizable unsaturated groups are present in the side chain with respect to the main chain of the urethane resin (A) in which urethane bonds are mainly present.
- the polymerizable unsaturated group derived from the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) undergoes radical polymerization when forming a coating film or the like. Thereby, the coating film excellent in hardness, elongation, and flexibility can be formed.
- R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
- pentaerythritol di (meth) acrylate has a structure in which R 1 in the general formula (1) has two atomic groups containing a polymerizable unsaturated group in the side chain of a propylene group having 3 carbon atoms.
- alkylene diol (a1-1) those having 2 or more and 5 or less polymerizable unsaturated groups are preferably used, and those having 2 or more and 3 or less polymerizable unsaturated groups are used. It is more preferable to obtain a urethane resin composition capable of forming a coating film excellent in hardness, elongation and flexibility.
- alkylene diol (a1-1) examples include pentaerythritol di (meth) acrylate [dimethylolpropane di (meth) acrylate], dimethylolmethane di (meth) acrylate (R 1 in the general formula (1) is , Those having 3 carbon atoms and two atomic groups having a polymerizable unsaturated group), diethylolmethane di (meth) acrylate, and diethylolpropane di (meth) acrylate (general formula (1 R 1 is a group having 5 carbon atoms and having two atomic groups having a polymerizable unsaturated group.), Dipropanolmethane di (meth) acrylate, dipropanolpropanedi (meth) acrylate (formula (1) R 1 in the intended 7 carbon atoms, is an atomic group having a polymerizable unsaturated group as it has two.) Di-butanol methane di (
- pentaerythritol di (meth) acrylate and dimethylolmethane di (meth) acrylate provides a urethane resin composition capable of forming a coating film excellent in hardness, elongation and flexibility. More preferable.
- alkylene diols (a1-1) can be used alone or in combination of two or more.
- (meth) acrylate” refers to either one or both of acrylate and methacrylate.
- R 1 and R 3 in the general formula (2) have a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
- R 1 and R 3 in the general formula (2) have a total of two or more structures having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group, preferably in the range of 2 or more and 5 or less, More preferably, it has in the range of 2 or more and 3 or less.
- R 2 in the general formula (2) represents an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentyl group.
- Examples of the oxyalkylene diol (a1-2) include bis (3-acryloyloxy-2-hydroxypropoxy) methane (R 1 and R 3 in the general formula (2) are those having 2 carbon atoms and are polymerizable. One having an unsaturated group and R 2 having one carbon atom), 1,2-bis (3-acryloyloxy-2-hydroxypropoxy) ethane (general formula (2 And R 1 and R 3 are those having 2 carbon atoms and having one atomic group having a polymerizable unsaturated group, and R 2 is having 2 carbon atoms.), 1, 3-bis (3-acryloyloxy-2-hydroxypropoxy) propane (in formula (2), R 1 and R 3 have 2 carbon atoms and have one atomic group having a polymerizable unsaturated group) in and, R 2 is the number of carbon atoms Is of.), 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane (formula (2) R 1 and R 3 in the intended 2 carbon atoms, a poly
- 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane provides a urethane resin composition capable of forming a coating film having excellent hardness, elongation and flexibility. More preferable.
- These oxyalkylene diols (a1-2) can be used alone or in combination of two or more.
- the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) are used in a total range of 0.1 to 49% by mass in the total amount of raw materials used in the production of the urethane resin (A). It is preferable from the viewpoint that a urethane resin composition capable of forming a coating film excellent in hardness, elongation and flexibility is obtained, and more preferably used in the range of 1 to 15% by mass.
- the total amount of the raw material used for manufacture of the said urethane resin (A) points out the total mass containing it, when a polyol (a1), polyisocyanate (a2), and a chain extender are used.
- polyol (a1) that can be used in the production of the urethane resin (A), in addition to the alkylene diol (a1-1) and the oxyalkylene diol (a1-2), other polyols may be used in combination as necessary. be able to.
- a polyol having an aromatic ring and / or a polyol having a sulfur atom is used for the purpose of imparting high refractive index performance to a coating film obtained using the urethane resin composition of the present invention. be able to.
- polyol having an aromatic ring examples include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, and alkylene oxide adducts of bisphenol. These polyols having an aromatic ring can be used alone or in combination of two or more.
- the alkylene oxide adduct of bisphenol is obtained by adding alkylene oxide to the phenolic hydroxyl group of bisphenol.
- Examples of the alkylene oxide adduct of bisphenol include an alkylene oxide adduct of bisphenol A, an alkylene oxide adduct of bisphenol F, and an alkylene oxide adduct of bisphenol S.
- Examples of the alkylene oxide include ethylene oxide and propion oxide.
- a polyol having a sulfur atom can be used in addition to the polyol having an aromatic ring.
- polyol having a sulfur atom examples include bis (2-hydroxyethyl) sulfide, 2,5-dihydroxy-1,4-dithiane, and the like.
- the other polyol may be hydrophilic, for example, for the purpose of imparting excellent water dispersion stability to the urethane resin (A).
- the polyol which has group is mentioned.
- polyol having a hydrophilic group examples include a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group. Of these, polyols having an anionic group are preferred.
- polyol having an anionic group examples include a polyol having a carboxyl group and a polyol having a sulfonic acid group.
- polyol having a carboxyl group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Among them, 2,2-dimethylol is preferable. Propionic acid is preferred. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group react with various polycarboxylic acids can also be used.
- polyol having a sulfonic acid group examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof; Polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, etc., and the polyester polyol and ⁇ -butyrolactone And polyester polyols obtained by reacting cyclic ester compounds such as ⁇ -valerolactone and ⁇ -caprolactone.
- dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and
- the anionic group is preferably partially or completely neutralized with a basic compound or the like in order to develop good water dispersibility.
- Examples of basic compounds that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine; sodium hydroxide, water Examples thereof include metal hydroxides including potassium oxide and lithium hydroxide.
- examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specific examples include N-methyl-diethanolamine and polyols obtained by reacting a compound having two epoxies with a secondary amine.
- the cationic group is preferably partially or completely neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid or the like.
- an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid or the like.
- the tertiary amino group as the cationic group is preferably partly or entirely quaternized.
- the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like, and dimethyl sulfate is preferable.
- examples of the polyol having a nonionic group include polyalkylene glycol having a structural unit derived from ethylene oxide.
- the polyol having a hydrophilic group is preferably used in the range of 1 to 20% by mass in the total amount of raw materials used in the production of the urethane resin (A), and further in terms of hardness, elongation and flexibility. Since a urethane resin composition capable of forming an excellent coating film can be obtained, it is more preferably used in the range of 1 to 15% by mass.
- examples of the other polyols include polyester polyols, polycarbonate polyols, polyether polyols and the like because they can form a coating film having excellent hardness, elongation and flexibility.
- polyester polyol and polycarbonate polyol are preferable.
- polyester polyol examples include a polyester polyol obtained by reacting a low molecular weight polyol and a polycarboxylic acid; a polyester polyol obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone; Examples include polyester polyols obtained by polymerization. These polyester polyols can be used alone or in combination of two or more.
- low molecular weight polyol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol and the like having a molecular weight of about 50 to 300.
- Aliphatic polyols such as cyclohexane dimethanol, and polyols having an aromatic structure such as bisphenol A and bisphenol F. Of these, 1,6-hexanediol and neopentyl glycol are preferable.
- polycarboxylic acid examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. And aromatic polycarboxylic acids such as anhydrides or esterified products thereof.
- the polycarbonate polyol is obtained by esterifying carbonic acid and a carbonate ester with a polyhydric alcohol.
- the polyhydric alcohol include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. These polycarbonate polyols can be used alone or in combination of two or more.
- polyether polyol examples include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.
- the compound having two or more active hydrogen atoms include propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, diester, and the like.
- examples include glycerin, trimethylolethane, trimethylolpropane, water, hexanetriol and the like.
- the alkylene oxide examples include propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These polyether polyols can be used alone or in combination of two or more.
- the polyester polyol, polycarbonate polyol and polyether polyol are preferably used in the range of 1 to 70% by mass, and in the range of 15 to 45% by mass, based on the total amount of raw materials used for the production of the urethane resin (A). It is more preferable to use in the case of being able to form a coating film having excellent hardness, elongation and flexibility.
- polyisocyanate (a2) used in the production of the urethane resin (A) examples include polyisocyanates having an aliphatic cyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; 4,4′-diphenylmethane Aromatic polyisocyanates such as diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Aliphatic polyiso, such as isocyanate Aneto and
- the polyol (a1) and the polyisocyanate (a2) As a method for producing the urethane resin (A) obtained by reacting the polyol (a1) and the polyisocyanate (a2), for example, in the absence of a solvent or in the presence of an organic solvent, the polyol (a1) and Examples thereof include a method in which the polyisocyanate (a2) is mixed and reacted at a reaction temperature in the range of about 50 to 150 ° C.
- the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is in the range of 0.8 to 2.5. It is preferably carried out in a range of 0.9 to 1.5.
- the coating film excellent in hardness, elongation, and flexibility can be formed, in addition to the said polyol (a1) and the said polyisocyanate (a2), it is necessary.
- the chain extender can be used.
- chain extender that can be used when producing the urethane resin (A)
- polyamine, hydrazine compounds, other active hydrogen atom-containing compounds, and the like can be used.
- polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. Moreover, these polyamines can be used alone or in combination of two or more.
- hydrazine compound examples include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; ⁇ -semicarbazide And propionic acid hydrazide.
- these hydrazine compounds can be used alone or in combination of two or more.
- Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, Glycols such as methylene glycol, glycerin and sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, phenol such as hydroquinone, and water
- the urethane resin composition of the present invention can be used alone or in combination of two or more within the range in which the storage stability does not deteriorate.
- Examples of the organic solvent that can be used in producing the urethane resin (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; acetonitrile and the like. Nitrile solvents; amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
- the organic solvent removes part or all of the organic solvent by, for example, distilling under reduced pressure during or after the production of the urethane resin (A). May be.
- urethane resin (A) obtained by the above method a resin having a weight average molecular weight in the range of 10,000 to 500,000 can be used because it can form a coating film having excellent hardness, elongation and flexibility. It is preferable to use those having a weight average molecular weight in the range of 20,000 to 200,000, and it is more preferable to use a weight average molecular weight in the range of 40,000 to 100,000.
- the urethane resin (A) it is preferable to use a resin having a urea bond because a coating film excellent in hardness, elongation and flexibility can be formed.
- urethane resin (A) one having a urea bond equivalent in the range of 500 to 50,000 is preferably used because a coating film excellent in hardness, elongation and flexibility can be formed.
- Examples of the polyfunctional acrylate (B) used in the present invention include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trimethylol ethylene oxide modified triacrylate, diglycerin ethylene oxide modified (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, pentaerythritol tri (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate Acrylate, glycerol tri (meth) acrylate, glycerol propoxytriacrylate, pentaeryth Tall ethylene oxide-modified tetraacrylate and the like.
- a urethane resin composition capable of forming a coating film with higher hardness can be obtained.
- dipentaerythritol penta (meth) acrylate is preferable.
- These polyfunctional acrylates can be used alone or in combination of two or more.
- the ratio of the polymerizable unsaturated bond in the polyfunctional acrylate (B) is preferably in the range of 4 to 12 mmol / g because a coating film having excellent hardness, scratch resistance and flexibility can be formed. A range of 4.3 to 11.8 mmol / g is more preferable.
- the hardness ratio of the urethane resin (A) and the polyfunctional acrylate (B) [polyfunctional acrylate (B) / urethane resin (A)] is in the range of 0.5 to 4, excellent hardness From the viewpoint that a coating film having scratch resistance and flexibility can be formed, the range of 1.4 to 3.5 is more preferable.
- the ratio of polymerizable unsaturated bonds in the sum of the urethane resin (A) and the polyfunctional acrylate (B) is in the range of 2.5 to 9.5 mmol / g. From the viewpoint of forming a coating film having flexibility and flexibility, more preferably in the range of 3.5 to 9 mmol / g, still more preferably in the range of 4 to 8.5 mmol / g.
- Examples of the method for producing the urethane resin composition of the present invention by dissolving or dispersing the urethane resin (A) and polyfunctional acrylate (B) obtained by the above method in the solvent (C) include, for example, the urethane resin (A ) Has a hydrophilic group, a method of neutralizing a part or all of the hydrophilic group and then mixing the neutralized product with the solvent (C) can be mentioned.
- Examples of the solvent (C) used in the present invention include water, organic solvents miscible with water, and mixtures thereof.
- the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone.
- only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
- the urethane resin composition of the present invention obtained by the above method comprises the urethane resin (A) and the polyfunctional acrylate (B) in a range of 5% by mass to 85% by mass with respect to the total amount of the urethane resin composition. It is preferable that it is contained in the range of 15% by mass to 50% by mass. Further, the urethane resin composition of the present invention obtained by the above method uses the one containing the solvent (C) in the range of 10% by mass to 90% by mass with respect to the total amount of the urethane resin composition. The content is preferably in the range of 45% by mass to 80% by mass.
- the urethane resin composition may contain an additive as necessary.
- the additive include a film forming aid, a filler, a thixotropic agent, a tackifier, a pigment and an antibacterial agent. Can be used as long as the object of the present invention is not impaired.
- the film forming aid examples include an anionic surfactant (dioctylsulfosuccinate ester soda salt, etc.), a hydrophobic nonionic surfactant (sorbitan monooleate, etc.), silicone oil, and the like.
- thixotropy-imparting agent examples include fatty acid, fatty acid metal salt, fatty acid ester, paraffin, resin acid, surfactant, polyacrylic acid and the like surface-treated filler, polyvinyl chloride powder, hydrogenated castor oil, Fine powder silica, organic bentonite, sepiolite and the like can be mentioned.
- pigment known and commonly used inorganic pigments and organic pigments can be used.
- examples of the inorganic pigment include titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, graphite and the like.
- organic pigment examples include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, Examples include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. Two or more kinds of these pigments can be used in combination. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.
- antibacterial agent examples include silver chloride, trifluanide, dichlorofluanide, fluorophorpet, zinc pyrithione, methyl 2-benzimidazole carbanate, 2- (4-thiazolyl) benzimidazole and the like.
- reaction accelerators metal reaction accelerators, metal salt reaction accelerators, amine reaction accelerators, etc.
- photopolymerization initiators include stabilizers (ultraviolet absorbers, antioxidants, Various additives such as heat stabilizers, moisture removal agents (4-paratoluenesulfonyl isocyanate, etc.), adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion promoters, antifoaming agents, leveling agents, etc. Is mentioned.
- photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [ 4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-o Oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy
- the urethane resin composition of the present invention can be suitably used, for example, as a coating agent capable of imparting surface protection and design properties to various substrates.
- Examples of the substrate on which the coating agent can be applied to form a coating film include a glass substrate, a metal substrate, a plastic substrate, paper, a wood substrate, and a fibrous substrate.
- the base material of porous body structures such as a urethane foam, can also be used.
- plastic substrate examples include a polycarbonate substrate, a polyester substrate, an acrylonitrile-butadiene-styrene substrate, a polyacryl substrate, a polystyrene substrate, a polyurethane substrate, an epoxy resin substrate, a polyvinyl chloride substrate, and a polyamide group. Materials and the like.
- a plated steel plate such as a galvanized steel plate or an aluminum-zinc alloy steel plate, an iron plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate, or the like can be used.
- the base material may be a planar material made of the material or may have a curved portion, or may be a base material made of fibers such as a nonwoven fabric.
- the coating agent of the present invention is applied, for example, directly on the surface of the base material or on the surface of the base material previously provided with a primer layer and the like, and then dried, and then the urethane resin (A) and the above-mentioned A coating film can be formed by advancing radical polymerization of the polymerizable unsaturated double group of the polyfunctional acrylate (B).
- a coating film is formed on the surface of the release paper by applying the coating agent on the release paper, then drying and curing, and a non-woven fabric obtained by applying an adhesive or an adhesive on the coating film.
- a film formed using the coating agent can be laminated on the surface of a desired substrate by laminating the substrate made of such fibers and peeling the release paper.
- Examples of the method for applying the coating agent on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
- examples of the method for curing the coating agent include a heating method and a method of irradiating active energy rays such as ultraviolet rays.
- the heating method varies depending on the type of radical polymerization initiator to be used. For example, by performing the heating at a temperature of about 100 ° C. to 150 ° C. for about 10 minutes to 30 minutes, the radical polymerization can be progressed and cured. it can.
- a method using a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED lamp is used.
- a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED lamp.
- the exposure dose of the actinic energy ray is preferably in the range of 50mJ / cm 2 ⁇ 5,000mJ / cm 2, more preferably in the range of 100mJ / cm 2 ⁇ 3,000mJ / cm 2, 100mJ / A range of cm 2 to 1000 mJ / cm 2 is particularly preferable.
- the above-mentioned ultraviolet irradiation amount is based on values measured in a wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).
- the thickness of the coating film that can be formed using the coating agent of the present invention can be appropriately adjusted according to the use of the substrate, but is usually preferably about 0.1 ⁇ m to 100 ⁇ m.
- articles provided with a coating film formed using the coating agent on the substrate are optical members such as liquid crystal displays and flexible displays, mobile phones, various plastic products including home appliances, It can be used as metal products such as automobile exteriors and building materials.
- Example 1 Preparation of urethane resin composition (1)
- a 2 liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was charged with 23.7 parts by mass of methyl ethyl ketone, 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass, polycarbonate polyol (Polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate, number average molecular weight 2000) 38.6 parts by weight, 1,6-hexanediol 3.9 parts by weight, Charge 0.0024 parts by mass of methylhydroquinone and 0.0242 parts by mass of 2,6-ter
- Example 2 Preparation of urethane resin composition (2)
- a 2 liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was charged with 23.7 parts by mass of methyl ethyl ketone, 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass, polyester polyol (Polyester polyol obtained by reacting 1,6-hexanediol, neopentyl glycol and adipic acid, number average molecular weight 2000) 38.6 parts by weight, 1,6-hexanediol 3.9 parts by weight, methylhydroquinone 0 0024 parts by mass and 0.0242 parts by mass of 2,6-tert-butyl
- Example 3 Preparation of urethane resin composition (3)
- a 2 liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was charged with 23.7 parts by mass of methyl ethyl ketone, 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass, polytetra Methylene ether glycol (number average molecular weight 2000) 38.6 parts by mass, 1,6-hexanediol 3.9 parts by mass, methylhydroquinone 0.0024 parts by mass, and 2,6-tert-butyl-p-cresol 0242 mass parts was charged, and it adjusted at 50 degreeC, stirring.
- Example 4 Preparation of urethane resin composition (4)
- a heating device a stirrer, a thermometer and a reflux condenser
- 61.5 parts by mass of methyl ethyl ketone 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass
- polycarbonate polyol Polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate, number average molecular weight 2000
- 1,6-hexanediol 0.04 parts by mass 0.0024 parts by mass of methylhydroquinone and 0.0242 parts by mass of 2,6-ter
- Example 5 Preparation of urethane resin composition (5)
- a heating device a stirrer, a thermometer and a reflux condenser
- 61.5 parts by mass of methyl ethyl ketone 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass
- polycarbonate polyol Polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate, number average molecular weight 2000
- 1,6-hexanediol 0.04 parts by mass 0.0024 parts by mass of methylhydroquinone and 0.0242 parts by mass of 2,6-ter
- Example 6 Preparation of urethane resin composition (6)
- a 2 liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was charged with 23.7 parts by mass of methyl ethyl ketone, 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass, polycarbonate polyol (Polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate, number average molecular weight 2000) 38.6 parts by weight, 1,6-hexanediol 3.9 parts by weight, Charge 0.0024 parts by mass of methylhydroquinone and 0.0242 parts by mass of 2,6-
- Example 7 Preparation of urethane resin composition (7)
- a heating device a stirrer, a thermometer and a reflux condenser
- 61.5 parts by mass of methyl ethyl ketone 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass
- polycarbonate polyol Polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate, number average molecular weight 2000
- 1,6-hexanediol 0.04 parts by mass 0.0024 parts by mass of methylhydroquinone and 0.0242 parts by mass of 2,6-ter
- Example 8 Preparation of urethane resin composition (8)
- a heating device a stirrer, a thermometer and a reflux condenser
- 23.7 parts by mass of methyl ethyl ketone pentaerythritol diacrylate (R 1 in the general formula (1) has 3 carbon atoms)
- 8.2 parts by mass of polycarbonate polyol reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate
- Polycarbonate polyol number average molecular weight 2000 47.8 parts by mass, 2.2 parts by mass of 1,6-hexanediol, 0.0024 parts by mass of methylhydroquinone, and 2,6-tert-butyl-p-cresol 0.0242 mass part was prepared and it adjusted at 50 degreeC, stirring.
- Example 9 Preparation of urethane resin composition (9)
- a 2 liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was charged with 23.7 parts by mass of methyl ethyl ketone, 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane (general formula (2 R 1 is 2 carbon atoms, R 2 is 4 carbon atoms, R 3 is 2 carbon atoms, 2 atomic groups having a polymerizable unsaturated group) 12.1 parts by mass, polycarbonate polyol (Polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate, number average molecular weight 2000) 38.6 parts by weight, 1,6-hexanediol 3.9 parts by weight, Charge 0.0024 parts by mass of methylhydroquinone and 0.0242 parts by mass of 2,6-
- Example 10 Preparation of urethane resin composition (10)
- a heating device a stirrer, a thermometer and a reflux condenser
- 61.5 parts by mass of methyl ethyl ketone 1,4-bis (3-acryloyloxy-2-hydroxyproxy) butane
- R 1 is 2 carbon atoms
- R 2 is 4 carbon atoms
- R 3 is 2 carbon atoms
- 12.1 parts by mass polycarbonate polyol
- Polycarbonate polyol Polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,5-pentanediol and diethyl carbonate, number average molecular weight 2000
- polytetramethylene ether glycol number average molecular weight 2000 21 0.7 part by weight, 1,6-hexanediol 0.04 part by weight
- a urethane resin composition (C2) having a nonvolatile content of 25% by mass was obtained by supplying 21.5 parts by mass of a 10% by mass isophoronediamine aqueous solution as a chain extender to the four-necked flask. .
- the hardness of the coating film constituting the article was measured by a method based on a JIS test method (JIS K5600-5-4: 1999) scratch hardness (pencil method).
- the surface of the hard coat layer was subjected to a steel wool test in which # 0000 steel wool was subjected to 100 reciprocating friction at a speed of 200 mm / sec while applying a load of 500 g / 3 cm 2 .
- the difference ( ⁇ H) was measured and evaluated according to the following evaluation criteria.
- ⁇ H The haze difference ( ⁇ H) before and after the steel wool resistance test was 3 or more and less than 8.
- ⁇ H Haze difference ( ⁇ H) before and after the steel wool resistance test was 8 or more and less than 10.
- X The haze difference ( ⁇ H) before and after the steel wool resistance test was 10 or more.
- the flexibility of the coating film constituting the article was evaluated according to the following evaluation criteria based on the measurement result according to the JIS K5600-5-1 bending resistance test method (mandrel diameter 2 mm).
- Table 1 shows the compositions and evaluation results of the urethane resin compositions (1) to (11) prepared in Examples 1 to 11.
- Table 2 shows the compositions and evaluation results of the urethane resin compositions (C1) to (C3) prepared in Comparative Examples 1 to 3.
- MEK in Tables 1 and 2 refers to methyl ethyl ketone.
- Examples 1 to 11 shown in Table 1 are examples using the urethane resin composition of the present invention. From the evaluation results of Examples 1 to 11, it was confirmed that the coating films obtained using the urethane resin composition of the present invention had excellent hardness, and excellent scratch resistance and flexibility.
- Comparative Example 1 shown in Table 2 the amount of the polymerizable unsaturated bond group in the total of the urethane resin and the polyfunctional acrylate is 1.6 mmol / g, and the urethane resin composition outside the scope of the present invention is used. This is an example. Although the coating film obtained using the urethane resin composition of Comparative Example 1 was excellent in flexibility, it was confirmed that the scratch resistance was remarkably insufficient.
- Comparative Example 2 is an example in which the amount of the polymerizable unsaturated bond group in the total of the urethane resin and the polyfunctional acrylate is 9.8 mmol / g, and the urethane resin composition outside the scope of the present invention is used. Although the coating film obtained using the urethane resin composition of Comparative Example 2 was excellent in hardness and scratch resistance, it was confirmed that the flexibility was remarkably insufficient.
- Comparative Example 3 is an example using a urethane resin composition containing no polyfunctional acrylate. Although the coating film obtained using the urethane resin composition of Comparative Example 3 was excellent in flexibility, it was confirmed that the hardness and scratch resistance were remarkably insufficient.
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Abstract
Description
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)38.6質量部、1,6-ヘキサンジオール3.9質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリエステルポリオール(1,6-ヘキサンジオールとネオペンチルグリコールとアジピン酸とを反応させて得られるポリエステルポリオール、数平均分子量2000)38.6質量部、1,6-ヘキサンジオール3.9質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリテトラメチレンエーテルグリコール(数平均分子量2000)38.6質量部、1,6-ヘキサンジオール3.9質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン61.5質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)43.4質量部、1,6-ヘキサンジオール0.04質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン61.5質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)43.4質量部、1,6-ヘキサンジオール0.04質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)38.6質量部、1,6-ヘキサンジオール3.9質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン61.5質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)43.4質量部、1,6-ヘキサンジオール0.04質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、ペンタエリスリトールジアクリレート(一般式(1)中のR1は、炭素原子数3のもので、重合性不飽和基を有する原子団を2つ有するものである。)8.2質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)47.8質量部、1,6-ヘキサンジオール2.2質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)38.6質量部、1,6-ヘキサンジオール3.9質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン61.5質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)21.7質量部、ポリテトラメチレンエーテルグリコール(数平均分子量2000)21.7質量部、1,6-ヘキサンジオール0.04質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン61.5質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)43.4質量部、1,6-ヘキサンジオール0.04質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)38.6質量部、1,6-ヘキサンジオール3.9質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン61.5質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)43.4質量部、1,6-ヘキサンジオール0.04質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
加熱装置、攪拌機、温度計及び還流冷却管を備えた2リットル4つ口フラスコに、メチルエチルケトン23.7質量部、1,4-ビス(3-アクリロイロキシ-2-ヒドロキシプロキシ)ブタン(一般式(2)中のR1は炭素原子数2個、R2は炭素原子数4個、R3は炭素原子数2個、重合性不飽和基を有する原子団2個)12.1質量部、ポリカーボネートポリオール(1,6-ヘキサンジオールと1,5-ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量2000)38.6質量部、1,6-ヘキサンジオール3.9質量部、メチルヒドロキノン0.0024質量部、及び、2,6-tert-ブチル-p-クレゾール0.0242質量部を仕込み、攪拌しながら50℃で調整した。
光重合開始剤(1-ヒドロキシ-シクロヘキシル-フェニル-ケトンとベンゾフェノンの混合物)を、実施例及び比較例で得た各ウレタン樹脂組成物に含まれるウレタン樹脂100質量部あたり4質量部混合し、それを、塗膜の膜厚が10μmとなるように、それぞれガラス基材の表面に塗布した。前記塗布物を140℃で5分間乾燥した後、高圧水銀灯(株式会社GSユアサ製)を用いて、400mJ/cm2の紫外線を2パス照射し、前記ガラス基材の表面に塗膜が積層した物品を得た。
光重合開始剤(1-ヒドロキシ-シクロヘキシル-フェニル-ケトンとベンゾフェノンの混合物)を、実施例及び比較例で得た各ウレタン樹脂組成物に含まれるウレタン樹脂100質量部あたり4質量部混合し、それを、塗膜の膜厚が10μmとなるように、それぞれガラス基材の表面に塗布した。前記塗布物を140℃で5分間乾燥した後、高圧水銀灯(株式会社GSユアサ製)を用いて、500mJ/cm2の紫外線を1パス照射することによって、前記ガラス基材の表面に塗膜が積層した物品を得た。
光重合開始剤(1-ヒドロキシ-シクロヘキシル-フェニル-ケトンとベンゾフェノンの混合物)を、実施例及び比較例で得た各ウレタン樹脂組成物に含まれるウレタン樹脂100質量部あたり4質量部混合し、それを、塗膜の膜厚が10μmとなるように、それぞれPETフィルム(150μm)の表面に塗布した。前記塗布物を100℃で30秒間乾燥した後、高圧水銀灯(株式会社GSユアサ製)を用いて、400mJ/cm2の紫外線を2パス照射し、前記PETフィルムの表面に塗膜が積層した物品を得た。
Claims (5)
- 下記一般式(1)で示される2つ以上の重合性不飽和基を有するアルキレンジオール(a1-1)または下記一般式(2)で示される2つ以上の重合性不飽和基を有するオキシアルキレンジオール(a1-2)を含有するポリオール(a1)と、ポリイソシアネート(a2)との反応物であるウレタン樹脂(A)、多官能アクリレート(B)、及び、溶媒(C)を含有するウレタン樹脂組成物であって、前記ウレタン樹脂(A)及び前記多官能アクリレート(B)の合計中の重合性不飽和結合の割合が2.5~9.5mmol/gの範囲であることを特徴とするウレタン樹脂組成物。
- 前記ウレタン樹脂(A)と前記多官能アクリレート(B)の質量比「多官能アクリレート(B)/ウレタン樹脂(A)」が、0.5~4の範囲である請求項1記載のウレタン樹脂組成物。
- 前記多官能アクリレート(B)中の重合性不飽和結合の割合が、4~12mmol/gの範囲である請求項1記載のウレタン樹脂組成物。
- 請求項1~3のいずれか1項記載のウレタン樹脂組成物からなるコーティング剤。
- 請求項4記載のコーティング剤の塗膜を有する物品。
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JP2015157962A (ja) * | 2014-01-22 | 2015-09-03 | Dic株式会社 | 硬化性組成物、その硬化物、成形品及びディスプレイ部材 |
WO2016002615A1 (ja) * | 2014-06-30 | 2016-01-07 | Dic株式会社 | 紫外線硬化性組成物 |
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WO2019182862A1 (en) | 2018-03-22 | 2019-09-26 | Aleo Bme, Inc. | Compositions and methods of making a thin film applications thereof |
EP3768730A4 (en) * | 2018-03-22 | 2021-12-29 | Aleo BME, Inc. | Compositions and methods of making a thin film applications thereof |
JP7331453B2 (ja) | 2019-05-17 | 2023-08-23 | Dic株式会社 | 多孔体の製造方法 |
Also Published As
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KR20180110154A (ko) | 2018-10-08 |
TW201802201A (zh) | 2018-01-16 |
US20200172656A1 (en) | 2020-06-04 |
TWI740919B (zh) | 2021-10-01 |
CN108884200B (zh) | 2021-01-26 |
CN108884200A (zh) | 2018-11-23 |
JPWO2017164002A1 (ja) | 2018-07-12 |
US11008417B2 (en) | 2021-05-18 |
KR102077485B1 (ko) | 2020-02-17 |
JP6344632B2 (ja) | 2018-06-20 |
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