JP4877431B2 - Acrylic-modified urethane urea resin composition and molded product obtained using the same - Google Patents

Description

  The present invention relates to an acrylic-modified urethane urea resin composition that can be used in various applications including, for example, molding materials, coating agents, and adhesives.

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

  The molded product is required to have various characteristics corresponding to its application. For example, when used for automobile interior materials, heat resistance at a level that does not cause discoloration or deformation of molded products when exposed to high temperatures in summer for a long time may be required. In such a case, there is a case where the strength and durability that can protect the contents from external factors are required.

  On the other hand, as the application of urethane-based molded products becomes more widespread, the molded products are required to have higher properties than ever before. For example, in the medical field, a packaged medical device is required to be sterilized by ultraviolet rays without opening, and such a packaging material has a high transmittance for ultraviolet rays and visible light in a relatively low wavelength region. There is a need for packaging materials.

  In recent years, with the rapid development of ultraviolet curable adhesives, from the viewpoint of improving the production efficiency of industrial products, for example, the adhesive is applied to the surface of a transparent adherend, and the other surface is coated with the adhesive. After the adherends are placed, they may be adhered by irradiating the adhesive layer with ultraviolet rays through the transparent adherend. At that time, when the transparent adherend is made of a material that can absorb ultraviolet rays or the like, the adhesive layer may not be sufficiently cured even when irradiated with a large amount of ultraviolet rays or the like. Therefore, there is a demand from the industry for a molded product that can be used for an adherend that can sufficiently transmit ultraviolet rays and visible light in a relatively low wavelength region.

  However, conventionally, it has been considered extremely difficult to improve the light transmittance in the low wavelength region of ultraviolet rays and visible light (approximately 380 nm), and for example, the light transmittance can be improved by only about 1%. However, since it took considerable effort and trial and error, the development of molding materials capable of forming molded articles having the light transmittance required by the industry is not progressing rapidly.

  Even under such circumstances, there have been reports on molding materials having excellent light transmittance. For example, a polyurethaneurea resin solution composed of an aliphatic monomer and / or an alicyclic monomer is used. In addition, it is known that a far ultraviolet ray transmissive film obtained by coating on a releasable substrate having a mirror surface and drying has excellent far ultraviolet ray permeability (for example, see Patent Document 1).

  Although the far ultraviolet ray transmissive film has good light transmittance to some extent, when used in a high temperature environment, the film may cause deformation or discoloration such as shrinkage of the film due to the influence of heat.

  As described above, there has not yet been found a molding material capable of forming a molded article such as a film having both excellent light transmittance in the low wavelength region of ultraviolet rays and visible light and excellent heat resistance. It is a fact.

Japanese Patent Laid-Open No. 62-156916

  The problem to be solved by the present invention is to form a molded product having excellent heat resistance at a level that does not cause deformation or discoloration due to the influence of heat, and is excellent in light transmittance in the low wavelength region of ultraviolet rays and visible light. It is to provide a possible resin composition.

  In order to solve the above-mentioned problems, the present inventors proceeded with studies based on the urethane urea resin described in Patent Document 1 and obtained acrylic resin obtained by introducing a specific amount of acryloyl group into the resin structure. It has been found that a modified urethane urea resin composition can achieve both excellent light transmittance and heat resistance.

That is, the present invention relates to an acrylic modified urethane urea resin (1) obtained by reacting a polyol (A), a polyisocyanate (B), a polyamine (C) and an acrylic compound (D) having an active hydrogen atom-containing group. and also contains a solvent (2), the equivalent weight of the acryloyl group derived from an acrylic compound (D) having said acryl-modified urethane urea resin Ri range der of 10000 to 50000,
With respect to the total mass of the polyol (A), polyisocyanate (B), polyamine (C), and acrylic compound (D) having an active hydrogen atom-containing group, which are raw materials used for the production of the acrylic-modified urethane urea resin, The present invention relates to an acrylic-modified urethane urea resin composition and a molded product obtained using the same, wherein the mass ratio of the urea bond structure in the raw material is 4 to 10% by mass .

  The acrylic-modified urethane urea resin composition of the present invention is excellent in light transmittance in the low wavelength region of ultraviolet rays and visible light, and has excellent heat resistance at a level that does not cause deformation or discoloration due to the influence of heat. Since a molded product can be formed, it can be used for the production of, for example, automobile parts, household electrical appliance parts, packaging materials, films and sheets, and leather-like sheet skin materials.

  Moreover, since the acrylic modified urethane urea resin composition of this invention is excellent in heat resistance as above-mentioned, it can be used for the surface coating agent, adhesive agent, etc. of various base materials, for example.

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

  The acrylic-modified urethane urea resin (1) used in the present invention is obtained by reacting a polyol (A), a polyisocyanate (B), a polyamine (C), and an acrylic compound (D) having an active hydrogen atom-containing group. Among the urethane urea resins having acryloyl groups derived from the acrylic compound (D), those having an equivalent weight of acryloyl groups in the range of 10,000 to 50,000.

  Here, the equivalent weight of the acryloyl group is an acrylic compound having a polyol (A), a polyisocyanate (B), a polyamine (C) and an active hydrogen atom-containing group constituting the acrylic-modified urethane urea resin (1). The value obtained by dividing the total mass with D) by the equivalent of the acryloyl group derived from the acrylic compound (D) present in the acrylic-modified urethane urea resin.

  An acrylic-modified urethane urea resin having an equivalent weight of the acryloyl group exceeding 50000 has almost no acryloyl group in the resin and may cause a significant decrease in heat resistance. On the other hand, the acrylic-modified urethane urea resin having an equivalent weight of less than 10,000 has its weight average molecular weight lowered to about less than 5000, which may cause a decrease in heat resistance. Therefore, as the acrylic-modified urethane urea resin (1) used in the present invention, it is possible to use a resin having an equivalent weight of acryloyl group of 10,000 to 50,000, which has light transmittance and heat resistance in a low wavelength region of ultraviolet light and visible light. It is indispensable to balance sex. As the acrylic-modified urethane urea resin (1), it is preferable to use a resin having an equivalent weight of 10,000 to 30,000.

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

  Moreover, as said acrylic modified urethane urea resin (1), what has 5-15 mass% urethane bond is used from a viewpoint of making compatible favorable heat resistance and light transmittance with the outstanding moldability. It is preferably 7 to 9% by mass. In addition, the mass ratio of the urethane bond includes the polyol (A), the polyisocyanate (B), the polyamine (C), and the active hydrogen atom-containing group which are raw materials used for the production of the acrylic-modified urethane urea resin (1). It is the ratio of the mass of the urethane bond structure which occupies in the said raw material with respect to the total mass with the acrylic compound (D) which has.

  Moreover, as said acrylic modified urethane urea resin (1), it is preferable to use what has a weight average molecular weight of 5000-200000 in order to maintain favorable moldability with excellent light transmittance and heat resistance. The range of 15000-200000 is more preferable. The weight average molecular weight of the acrylic-modified urethane urea resin is a value determined by styrene conversion using gel permeation chromatography (GPC) and tetrahydrofuran as an eluent.

  Next, the polyol (A) used for manufacture of the said acrylic modified urethane urea resin (1) is demonstrated.

  As the polyol (A), various types can be used, but those having a hydroxyl value in the range of 30 to 230 mgKOH / g are preferable, and those in the range of 50 to 230 mgKOH / g. More preferably it is used. The hydroxyl value of the polyol (A) is a value measured according to JIS K0070.

  As the polyol (A), for example, polyester polyol, polycarbonate polyol, polyether polyol, acrylic polyol, and the like can be used. Among them, it is preferable to use those having no aromatic cyclic structure. It is preferable for further improving.

  Examples of the polyester polyol include a ring-opening polymerization reaction of an aliphatic polyester polyol obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, or a cyclic ester compound such as ε-caprolactone or γ-valerolactone. Polyester obtained, these copolyesters, etc. can be used.

  Examples of the low molecular weight polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, and 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3- Propanediol, neopentyl glycol, 2-butyl 2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, Aliphatic polyols such as ditrimethylolpropane, tritrimethylolpropane, pentaerythritol, aliphatic cyclic structure-containing polyols such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A, alkylene oxide adducts of bisphenol A, bisphenol A polyol such as an alkylene oxide adduct of S or bisphenol S can be used. Among them, an aliphatic or aliphatic cyclic structure-containing polyol is preferably used, and an aliphatic diol is more preferably used.

  Examples of the polycarboxylic acid include fatty acids such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid aliphatic polycarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and cyclohexanetricarboxylic acid. Cyclic polycarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid Aromatic polycarboxylic acids such as these and their anhydrides or ester derivatives can be used alone or in combination of two or more, and it is preferable to use aliphatic polycarboxylic acids, and to use aliphatic dicarboxylic acids It is more preferable.

  As the polyester polyol, it is preferable to use a polyester polyol having no aromatic cyclic structure, and it is more preferable to use a polyester polyol obtained by reacting the aliphatic polyol and the aliphatic polycarboxylic acid. In particular, it is possible to use a product obtained by reacting an aliphatic polyol having 2 to 6 carbon atoms with an aliphatic polycarboxylic acid having 2 to 6 carbon atoms. It is particularly preferable for imparting light transparency.

  Moreover, as a polycarbonate polyol which can be used for the said polyol (A), what is obtained by making carbonate and / or phosgene react with the polyol mentioned later can be used, for example.

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

  Examples of the polyol that can react with the carbonate ester or phosgene include, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, and tripropylene glycol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2 -Methyl-1,3-propanediol, neo Nthyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octane Dihydroxy compounds of relatively low molecular weight such as diol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydroquinone, resorcin, bisphenol A, bisphenol F, 4,4′-biphenol, polyethylene glycol, polypropylene glycol , Polyether polyols such as polytetramethylene glycol, and polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used. Of these, aliphatic diols are preferred. Ku, it is more preferable to use 1,6-hexanediol.

  The polycarbonate polyol is preferably used because it can further improve the heat resistance and light transmittance of a molded product formed using the resulting acrylic-modified urethane urea resin composition. Especially, it is more preferable to use the polycarbonate polyol which does not have an aromatic cyclic structure, and it is especially preferable to use a 1, 6- hexanediol type polycarbonate polyol.

  Further, as the polyether polyol that can be used for the polyol (A), for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator is used. be able to.

  Examples of the initiator include water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexane Diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, 2-butyl-2-ethyl -1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, glycerin, diglycerin, trimethylolpropane, Ditrimethylolpropane, tritrimethylolpropane, 1,2,6-hexanetriol, triethanolamine, triisopropanolamine, pentaerythritol, dipentaerythritol, sorbitol, saccharose, ethylenediamine, N-ethyldiethylenetriamine, 1,2-diamino Propane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, diethylenetriamine, phosphoric acid, acidic phosphate ester and the like can be used.

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

  The polyol (A) is a total mass of the polyol (A), the polyisocyanate (B), the polyamine (C), and the acrylic compound (D), which are raw materials used for the production of the resulting acrylic-modified urethane urea resin (1). It is preferable to use in the range of 40-80 mass%.

Next, the polyisocyanate (B) will be described.
Examples of the polyisocyanate (B) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, and 4,4′-dicyclohexylmethane diisocyanate. Aliphatic or aliphatic cyclic structure-containing diisocyanates such as xylylene diisocyanate and tetramethyl xylylene diisocyanate can be used alone or in combination of two or more. Among them, it is preferable to use an aliphatic cyclic structure-containing diisocyanate in order to improve light transmittance and heat resistance in a low wavelength region of ultraviolet light and visible light, and 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate. More preferably, is used. In particular, when improving heat resistance, it is particularly preferable to use 4,4′-dicyclohexylmethane diisocyanate.

  The polyisocyanate (B) is a total of polyol (A), polyisocyanate (B), polyamine (C) and acrylic compound (D) which are raw materials used for the production of the resulting acrylic-modified urethane urea resin (1). It is preferable to use in the range of 15-50 mass% with respect to the mass.

  Next, the polyamine (C) will be described.

  The polyamine (C) is used for introducing a urea bond into the acrylic-modified urethane urea resin (1).

  Examples of the polyamine (C) include ethylenediamine, propylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, diaminocyclohexane, methyldiaminocyclohexane, biperazine, and norbornenediamine. Among them, use of an aliphatic cyclic structure-containing polyamine such as isophorone diamine, 4,4′-dicyclohexylmethane diamine, norbornene diamine provides light transmittance in a low wavelength region of ultraviolet light or visible light. It is preferable for further improvement, it is more preferable to use an aliphatic cyclic structure-containing diamine, and isophorone diamine is particularly preferable.

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

  Next, the acrylic compound (D) will be described.

  The acrylic compound (D) having an active hydrogen atom-containing group used in the present invention is used for introducing an acryloyl group into the acrylic-modified urethane urea resin (1) and can react with an isocyanate group. Those having an active hydrogen atom-containing group are used. Specifically, it is preferable to use a hydroxyl group-containing acrylic compound.

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

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

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

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

  Further, a part of the acrylic compound (D) may be present in an unreacted state in the acrylic-modified urethane urea resin composition of the present invention. That is, the acrylic modified urethane urea resin composition of the present invention may contain the unreacted acrylic compound (D) together with the acrylic modified urethane urea resin (1).

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

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

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

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

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

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

  In the production method (i), the polyol (A) and the polyisocyanate (B) are reacted under the solvent (2) to obtain a urethane prepolymer having an isocyanate group at the molecular end, and then the urethane prepolymer. In this method, an acrylic modified urethane urea resin (1) is produced by reacting a polymer, the polyamine (C) and the acrylic compound (D).

  In the reaction of the polyol (A) and the polyisocyanate (B), the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (A) and the isocyanate group of the polyisocyanate (B) is 1.1 /. It is preferably carried out in the range of 1.0 to 5.0 / 1.0, and more preferably in the range of 1.5 / 1.0 to 3.0 / 1.0. The reaction between the polyol (A) and the polyisocyanate (B) is preferably carried out under a condition of 20 to 120 ° C. for about 30 minutes to 24 hours.

  The reaction of the urethane prepolymer having an isocyanate group at the molecular end obtained by the reaction of the polyol (A) and the polyisocyanate (B), the polyamine (C) and the acrylic compound (D) is, for example, The urethane prepolymer and the polyamine (C) are fed together or sequentially to produce a urethane urea prepolymer, and the urethane urea prepolymer and the acrylic compound (D) are reacted to produce an acrylic modification. Urethane urea resin (1) can be produced. At that time, the equivalent ratio [amino group / isocyanate group] of the isocyanate group of the urethane prepolymer and the amino group of the polyamine (C) is in the range of 0.70 / 1.0 to 0.99 / 1.0. Preferably there is. Alternatively, the urethane prepolymer, the polyamine (C), and the acrylic compound (D) may be mixed together or sequentially and reacted at about 20 to 80 ° C. for about 1 to 3 hours. .

  Moreover, the said manufacturing method (ii) obtains the polyurea prepolymer which has an isocyanate group in a molecular terminal by making the said polyisocyanate (B) and the said polyamine (C) react under the said solvent (2), This is a method for producing an acrylic-modified urethane urea resin (1) by reacting the polyurea prepolymer, the polyol (A) and the acrylic compound (D).

  In the reaction of the polyisocyanate (B) and the polyamine (C), the equivalent ratio [isocyanate group / amino group] of the isocyanate group of the polyisocyanate (B) and the amino group of the polyamine (C) is 1. It is preferable to carry out in the range of 1 / 1.0 to 5.0 / 1.0.

  The reaction of the polyurea prepolymer having an isocyanate group at the molecular end obtained by the reaction of the polyisocyanate (B) and the polyamine (C), the polyol (A) and the acrylic compound (D), For example, the polyurea prepolymer and the polyol (A) are fed together or sequentially to react to produce a urethane urea prepolymer having an isocyanate group at the molecular end, and the urethane urea prepolymer and the acrylic compound (D ) Can be reacted to produce an acrylic-modified urethane urea resin (1). Moreover, it can also manufacture by making the said polyurea prepolymer, the said polyol (A), and the said acrylic compound (D) react collectively and sequentially.

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

  The acrylic modified urethane urea resin composition of the present invention containing the acrylic modified urethane urea resin (1) and the solvent (2) obtained by the above method may contain a curing agent or a curing accelerator as necessary. good.

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

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

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

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

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

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

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

  The acrylic modified urethane urea resin composition of the present invention may contain other additives in addition to those described above as long as the effects of the present invention are not impaired.

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

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

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

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

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

  In addition, as described above, the acrylic-modified urethane urea resin composition can be used for various applications such as a coating material and an adhesive as well as a molding material for forming various molded products. Among them, the acrylic-modified urethane urea resin composition is excellent in predetermined light transmittance, so that various industrial products such as building members such as counters and bathtubs, automobile members, medical members, and electronic equipment members that are required to have design properties. It is preferable to use it for the production of a molded product such as a member constituting the.

  Examples of a method for producing a molded product by molding the acrylic-modified urethane urea resin composition include, for example, a press molding method using a heating mold, an injection molding method, an RTM (resin transfer molding) molding method, a continuous molding method, and a drawing method. A molding method or the like can be applied.

  Examples of a method for producing a film or sheet-like molded product using the acrylic-modified urethane urea resin composition include, for example, the acrylic-modified urethane urea resin composition on the surface of a release substrate, for example, a curtain flow coater method or a die coater. A method of coating by a slit coater method, a knife coater method, a roll coater method or the like such as a method, drying as required, and then irradiating or heating with ultraviolet rays or the like is preferable. The drying may be natural drying at normal temperature, but may be heat-dried. The heat drying is usually preferably performed at 40 to 250 ° C. for about 1 to 600 seconds.

  The molded product obtained by the above method is excellent in light transmittance, particularly excellent in light transmittance in the low wavelength region of ultraviolet rays and visible light, and also excellent in heat resistance. It can be used in various applications such as molded articles, building parts, automobile parts, home appliance parts, medical instrument parts, various containers, packaging applications, and skin layers and intermediate layer forming films or sheets of leather-like sheets.

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

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

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

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

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

Next, the urethane-urea prepolymer solution, 8.1 parts by mass of 2-hydroxyethyl acrylate, and 241.2 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic modified urethane urea is obtained. Resin composition (I) (equivalent weight of acryloyl group; 1.15 × 10 ⁴ , weight average molecular weight; 20000, nonvolatile content: 25% by mass) was obtained.

[Example 2]
Polyester polyol (hydroxyl value: obtained by reacting 1,4-butanediol and adipic acid with a 5-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 112.2) Preparation of 500.0 parts by mass, addition of 222.2 parts by mass of isophorone diisocyanate and 180.6 parts by mass of toluene, and reaction at 80 ° C. for 3 hours while suppressing heat generation, resulted in an isocyanate group at the molecular end. A toluene solution of a urethane prepolymer having the following was obtained.

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

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

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

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

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

[Example 4]
Polyester polyol (hydroxyl value: obtained by reacting 1,4-butanediol and adipic acid with a 5-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 112.2) Charge 500.0 parts by mass, add 262.4 parts by mass of 4,4′-dicyclohexylmethane diisocyanate and 190.6 parts by mass of toluene, and react at 80 ° C. for 3 hours while suppressing heat generation. Thus, a toluene solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

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

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

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

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

Next, the urethane-urea prepolymer solution, 3.5 parts by mass of 2-hydroxyethyl acrylate, and 240.8 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic-modified urethane. A urea resin composition (V) (equivalent weight of acryloyl group; 2.66 × 10 ⁴ , weight average molecular weight; 63000, nonvolatile content; 25% by mass) was obtained.

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

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

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

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

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

  Next, the urethane urea prepolymer solution and 240.4 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby the urethane urea resin composition (VII) (equivalent weight of acryloyl group; -, Weight average molecular weight; 62000, non-volatile content; 25 mass%).

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

  Next, the toluene solution cooled to 40 ° C., 1455.9 parts by mass of N, N-dimethylformamide, and 547.4 parts by mass of toluene were mixed, and then mixed with 63.4 parts by mass of isophoronediamine. By reacting at 60 ° C. for 3 hours, a urethane urea prepolymer solution having an isocyanate group at the molecular end was obtained.

Next, the urethane-urea prepolymer solution, 23.2 parts by mass of 2-hydroxyethyl acrylate and 242.6 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby acrylic modified urethane is obtained. A urea resin composition (VIII) (equivalent weight of acryloyl group; 4.05 × 10 ³ , weight average molecular weight; 12000, nonvolatile content: 25% by mass) was obtained.

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

  Next, the urethane prepolymer solution having an isocyanate group at the molecular end by mixing the toluene solution cooled to 40 ° C., 1509.0 parts by mass of N, N-dimethylformamide, and 574.0 parts by mass of toluene. Got.

Next, the urethane prepolymer solution, 116.1 parts by mass of 2-hydroxyethyl acrylate, and 251.5 parts by mass of sec-butanol are mixed and reacted at 70 ° C. for about 1 hour, whereby an acrylic modified urethane resin is obtained. A composition (IX) (equivalent weight of acryloyl group; 8.38 × 10 ² , weight average molecular weight; 6100, nonvolatile content; 25% by mass) was obtained.

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

[Method for producing molded product (film)]
2 parts by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd., photopolymerization initiator) is mixed with 100 parts by mass of the solid content of the resin compositions obtained in the above Examples and Comparative Examples and stirred for 10 minutes. To obtain a coating solution.

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

[Evaluation method of light transmittance]
The light transmittance (%) of the film prepared above was measured in a wavelength range of 200 nm to 900 nm using a V-570 spectrophotometer manufactured by JASCO Corporation, and at wavelengths of 380 nm, 350 nm, and 300 nm. Evaluation was based on the light transmittance at the time of measurement. A light transmittance of 85% or more at a wavelength of 380 nm, a light transmittance of 80% or more at a wavelength of 350 nm, and a light transmittance of 70% or more at a wavelength of 300 nm was evaluated as being excellent in light transmittance.
In addition, what could not produce a film due to poor moldability was evaluated as “x” because the light transmittance could not be measured.

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

  Those having a flow start temperature of approximately 170 ° C. or higher were evaluated as having excellent heat resistance. Moreover, since the process start temperature was not measurable by the said method, what was not able to manufacture a film because moldability was bad was evaluated, and heat resistance was evaluated as "x".

Abbreviations in Tables 1 and 2 will be described.
“BG-AA” is a polyester polyol (hydroxyl value: 112.2) obtained by reacting 1,4-butanediol and adipic acid.
“HG-PC” is “Nipporan 981” (1,6-hexanediol-based polycarbonate polyol) manufactured by Nippon Polyurethane Industry Co., Ltd.
“IPDI” is isophorone diisocyanate.
“H12MDI” is 4,4′-dicyclohexylmethane diisocyanate.
“IPDA” is isophoronediamine.
“HEA” is 2-hydroxyethyl acrylate.

  The acrylic-modified urethane urea resin composition of the present invention is excellent in light transmittance in the low wavelength region of ultraviolet rays and visible light, and has excellent heat resistance at a level that does not cause deformation or discoloration due to the influence of heat. Since a molded product can be formed, it can be used for the production of, for example, automobile parts, household electrical appliance parts, packaging materials, films and sheets, and leather-like sheet skin materials.

  Moreover, since the acrylic modified urethane urea resin composition of this invention is excellent in heat resistance as above-mentioned, it can be used for the surface coating agent, adhesive agent, etc. of various base materials, for example.

Claims (11)

Contains acrylic modified urethane urea resin (1) and solvent (2) obtained by reacting polyol (A), polyisocyanate (B), polyamine (C) and acrylic compound (D) having an active hydrogen atom-containing group to become the equivalent weight of the acryloyl group derived from an acrylic compound (D) having said acryl-modified urethane urea resin Ri range der of 10000 to 50000,
Total mass of the polyol (A), the polyisocyanate (B), the polyamine (C), and the acrylic compound (D) having an active hydrogen atom-containing group, which are raw materials used for the production of the acrylic-modified urethane urea resin (1) An acrylic-modified urethane urea resin composition , wherein a mass ratio of a urea bond structure in the raw material is 4 to 10% by mass . The mass ratio of the acrylic modified urethane urea resin (1) and the solvent (2) in the acrylic modified urethane urea resin composition is (1) / (2) = 10-50 / 90-50. The acrylic-modified urethane urea resin composition according to 1. The acrylic modified urethane urea resin composition according to claim 1 or 2, wherein the polyol (A) has a hydroxyl value of 30 to 230 mgKOH / g. The acrylic modified urethane urea resin composition according to any one of claims 1 to 3, wherein the polyol (A) is a polyol having no aromatic cyclic structure. The acrylic modified urethane urea resin composition according to claim 4, wherein the polyol having no aromatic cyclic structure is at least one selected from the group consisting of polyester polyols and polycarbonate polyols. The acrylic modified urethane urea resin composition according to any one of claims 1 to 5, wherein the polyisocyanate (B) is an aliphatic cyclic structure-containing polyisocyanate. The acrylic modified urethane urea resin composition according to claim 6, wherein the aliphatic cyclic structure-containing polyisocyanate is at least one selected from the group consisting of 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate. The acrylic modified urethane urea resin composition according to any one of claims 1 to 7, wherein the polyamine (C) is an aliphatic cyclic structure-containing polyamine. The acrylic modified urethane urea resin composition according to claim 1, wherein the acrylic compound (D) is a hydroxyl group-containing acrylic acid alkyl ester. The acrylic modified urethane urea resin composition according to any one of claims 1 to 9, wherein the acrylic modified urethane urea resin has a weight average molecular weight of 5,000 to 200,000. The molded product obtained by shape | molding the acrylic modified urethane urea resin composition of any one of Claims 1-10.