JP2012017433A - Urethane resin composition, coating agent, hard coating agent, and cured product obtained by using the same, and method for producing cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane resin composition that enables formation of a molded article having extremely high hardness and excellent scratch resistance.SOLUTION: The urethane resin composition contains an alcohol-soluble urethane resin (A) having an oxyethylene structure and a hydrolyzable silyl group, at least one kind of hydrolyzable group-containing compound (B) selected from a group consisting of metal alkoxide (B-1) and its condensate (B-2), and an alcohol (C). The total mass of silicon atoms and oxygen atoms constituting the hydrolyzable silyl group possessed by the alcohol-soluble urethane resin (A) and of metal atoms and oxygen atoms possessed by the hydrolyzable group-containing compound (B) is 50 mass% or more and 95 mass% or less with respect to the total mass of the alcohol-soluble urethane resin (A) and the hydrolyzable group-containing compound (B).

Description

  The present invention relates to a urethane resin composition that can be used in various applications including, for example, coating agents and molding materials.

  As urethane resin compositions, solvent-based, water-based, and solvent-free ones are conventionally known, and they are used in various applications including molding materials such as films and sheets, adhesives, and coating agents. Yes.

  Among these, solvent-based urethane resin compositions are still widely used because they can generally form a film having excellent durability and water resistance as compared with water-based urethane resin compositions.

  However, from the viewpoint of reducing environmental impact in recent years, the use of solvent-based urethane resin compositions tends to be avoided, and in particular, urethane resin compositions containing strong solvents such as dimethylformamide have adverse effects on the environment and the human body. Therefore, the development of a urethane resin composition excellent in durability and water resistance in place of the solvent-based urethane resin composition is demanded by the industry.

  On the other hand, in the fields of use of the urethane resin composition as described above, for example, surface protection materials such as liquid crystal displays and touch panel devices, medical materials such as artificial bones and artificial teeth, automobile parts, From the viewpoint of preventing deformation and scratches with time, development of a urethane resin composition capable of forming a molded product having high hardness and excellent scratch resistance is required.

  As a urethane resin composition capable of forming a molded product having a relatively high hardness, for example, a composition for an organic-inorganic hybrid polyurethane comprising a polyurethane having alkoxysilyl groups at both ends and a hydrolyzable alkoxysilane is known. (For example, refer to Patent Document 1).

  Although the composition for organic / inorganic hybrid polyurethane can form a molded article having relatively good hardness, it has a very high hardness that can be used for surface protective materials such as touch panel devices and medical materials such as artificial bones. In some cases, the molded product could not be formed.

  In addition, automobile members, various window glasses, and the like may be required to have excellent scratch resistance that is difficult to be scratched even when a very hard object such as a stone or a metal piece comes into contact therewith.

  However, when a metal piece or the like comes into contact with the surface of a molded product obtained by using the composition described in the above-mentioned document 1, a significant scratch occurs on the surface, causing a defective appearance or the like of the molded product. There was a case.

  In addition, as described above, the urethane resin composition using a strong solvent such as dimethylformamide as a solvent is being avoided from the viewpoint of reducing the environmental load. In some cases, the solvent was not sufficiently dissolved in the alcohol solvent, resulting in a decrease in storage stability and the like. In order to impart good storage stability, it may be necessary to use a strong solvent such as methyl ethyl ketone or toluene together with the alcohol solvent.

  As described above, an alcohol-soluble resin composition having an extremely high hardness compared to the prior art and capable of forming a molded product that does not scratch even when scraped with a metal or the like is provided by the industry. Although it was sought after, it was still not found.

JP 2000-63661 A

  The problem to be solved by the present invention is to provide a urethane resin composition capable of forming a cured product having extremely high hardness and excellent scratch resistance.

  In order to further increase the hardness of the obtained cured product, the present inventors have considered that it would be effective to increase the content of the inorganic component contained in the cured product. Specifically, on the basis of the composition described in Patent Document 1, it was studied to increase the amount of hydrolyzable alkoxysilane used.

  However, only by increasing the amount of the hydrolyzable alkoxysilane used, the storage stability of the resulting resin composition is remarkably reduced, or the film forming property during coating is significantly reduced. An improvement in scratch resistance could not be realized.

  Accordingly, the present inventors have considered and considered that it is important to select a urethane resin to be used in combination with the hydrolyzable alkoxysilane and the like in order to increase the content of inorganic components.

  As a result, when an alcohol-soluble urethane resin having an oxyethylene structure and a hydrolyzable silyl group is used, it is possible to increase the content of inorganic components such as the hydrolyzable alkoxysilane, which is more than conventional. The inventors have found a urethane resin composition that has high hardness at each stage and can be dissolved in an alcohol solvent without using a strong solvent such as toluene.

  That is, the present invention is selected from the group consisting of an alcohol-soluble urethane resin (A) having an oxyethylene structure and a hydrolyzable silyl group, a metal alkoxide (B-1) and a condensate (B-2) thereof. A urethane resin composition containing at least one hydrolyzable group-containing compound (B) and an alcohol (C), comprising the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) The total mass of the silicon atoms and oxygen atoms to be produced and the metal atoms and oxygen atoms of the hydrolyzable group-containing compound (B) is such that the alcohol-soluble urethane resin (A) and the hydrolyzable group-containing compound ( The present invention relates to a urethane resin composition characterized by being 50% by mass or more and 95% by mass or less with respect to the total mass of B) and a cured product obtained by using the urethane resin composition.

  In addition, the present invention applies the composition obtained by mixing water and an acid catalyst to the urethane resin composition or the urethane resin composition, if necessary, on the surface of the substrate. By removing the alcohol (C) contained in the coating layer, the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) is hydrolyzed, and the metal alkoxide (B -1) and a hydroxyl group produced by hydrolysis of an alkoxy group bonded to a metal atom of one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the condensate (B-2) The present invention relates to a method for producing a cured product characterized by reacting to form a bond.

  Since the urethane resin composition of the present invention can form a cured product such as a film or various molded products having extremely high hardness and excellent scratch resistance as compared with conventional ones, it is used, for example, as a coating agent or a molding material. be able to. In addition, the urethane resin composition of the present invention is superior in solvent resistance to methyl ethyl ketone and various alcohols without damaging the excellent hardness and high scratch resistance, and can be applied to various substrates including glass. On the other hand, a cured product such as a film or molded product having excellent adhesion can be formed.

  Therefore, the urethane resin composition of the present invention is, for example, a surface coating of parts constituting automobiles, railways, etc., a surface coating of light receiving surfaces of photovoltaic power generation devices such as solar power generation devices, a surface coating of electronic components, etc., wall materials Can be used for molding materials such as coating materials used for surface coatings such as glass, flooring and window glass, and their adhesives, medical materials such as artificial bones and artificial teeth, automobile parts, household appliance parts and electronic materials It is.

  The present invention is one selected from the group consisting of an alcohol-soluble urethane resin (A) having an oxyethylene structure and a hydrolyzable silyl group, a metal alkoxide (B-1) and a condensate (B-2) thereof. A urethane resin composition containing the hydrolyzable group-containing compound (B), an alcohol (C), and other components as necessary, the alcohol-soluble urethane resin (A) having The total mass of the silicon atom and oxygen atom constituting the hydrolyzable silyl group and the metal atom and oxygen atom of the hydrolyzable group-containing compound (B) is the alcohol-soluble urethane resin (A) and the above It is a urethane resin composition characterized by being 50 mass% or more and 95 mass% or less with respect to the total mass of the hydrolyzable group-containing compound (B).

  The urethane resin composition of the present invention uses the alcohol (C) as a solvent, the alcohol-soluble urethane resin (A), the metal alkoxide (B-1), and a condensate (B) in the alcohol (C). -2). One or more hydrolyzable group-containing compounds (B) selected from the group consisting of 2) are dissolved or dispersed.

  Here, at least one hydrolyzable group-containing compound (B) selected from the group consisting of the alcohol-soluble urethane resin (A), the metal alkoxide (B-1) and the condensate (B-2) thereof. ) Are difficult to react in the alcohol (C) as a solvent, and many of them are often present independently in the alcohol (C).

  Specifically, the hydrolyzable silyl group possessed by the alcohol-soluble urethane resin (A) is not hydrolyzed in the alcohol (C) and hardly forms a silanol group. One or more hydrolyzable group-containing compounds (B) selected from the group consisting of the metal alkoxide (B-1) and the condensate (B-2) thereof also have an alkoxy group bonded to the metal atom. Does not decompose and hardly forms hydroxyl groups. As a result, at least one hydrolyzable group-containing compound (B) selected from the group consisting of the alcohol-soluble urethane resin (A), the metal alkoxide (B-1) and the condensate (B-2) thereof. It is difficult to react in alcohol (C).

  As a result, the urethane resin composition of the present invention can maintain good storage stability and coating workability for a long period of time without causing an increase in viscosity over time.

  In addition, if the urethane resin composition of this invention is a range which does not impair the said favorable storage stability etc., the said alcohol soluble type urethane resin (A), the said metal alkoxide (B-1), and its condensate will be sufficient as it. Even when one or more hydrolyzable group-containing compounds (B) selected from the group consisting of (B-2) are dissolved or dispersed in alcohol (C) in a partially bonded state. Good.

  The urethane resin composition of the present invention preferably has a viscosity in the range of 500 to 10,000 mPa · s from the viewpoint of good coating workability and the like.

  On the other hand, when the urethane resin composition of the present invention is applied to the surfaces of various substrates, dried, and the alcohol (C) contained in the coating layer is volatilized and removed, the alcohol-soluble urethane resin (A) is hydrolyzed. The functional silyl group is hydrolyzed by moisture (water) in the atmosphere or intentionally added water to form a silanol group. In addition, the one or more hydrolyzable group-containing compound (B) selected from the group consisting of the metal alkoxide (B-1) and the condensate (B-2) thereof has an alkoxy group bonded to the metal atom. Decomposes to form hydroxyl groups.

  And between the hydroxyl groups formed in one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the metal alkoxide (B-1) and its condensate (B-2), or the hydroxyl groups And a silanol group in the alcohol-soluble urethane resin (A) are condensed, and a cured product such as a film or a molded product having extremely high hardness and excellent scratch resistance can be formed.

  The urethane resin composition of the present invention comprises a silicon atom and an oxygen atom constituting the hydrolyzable silyl group of the alcohol-soluble urethane resin (A), the metal alkoxide (B-1) and a condensate thereof (B -2) The total mass of the metal atom and oxygen atom of one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the alcohol-soluble urethane resin (A) and the hydrolyzable The alcohol-soluble urethane resin (A) and the hydrolyzable group-containing compound (B) are used in combination within a range of 50% by mass to 95% by mass with respect to the total mass of the group-containing compound (B). It is important to.

  Even when a urethane resin composition having a mass ratio of less than 50% by mass is used, a cured product having a certain degree of good hardness can be formed. However, for example, in “scratch hardness (pencil method)” performed in accordance with a method defined in JISK5600, a cured product having an extremely high hardness of 9H to 7H may not be formed. Moreover, the hardened | cured material obtained using the urethane resin composition whose said mass ratio is less than 50 mass% may generate | occur | produce a remarkable crack when the surface is rubbed with a metal etc.

  On the other hand, when a urethane resin composition having a blending ratio of more than 95% by mass is used, the storage stability of the resulting resin composition is remarkably lowered, and the film forming property and the molding processability are significantly reduced. In some cases, a cured product such as a film or a molded product cannot be obtained.

  Therefore, the urethane resin composition of the present invention includes a silicon atom and an oxygen atom constituting the hydrolyzable silyl group of the alcohol-soluble urethane resin (A), the metal alkoxide (B-1) and a condensation thereof. The total mass of the metal atom and oxygen atom of one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the product (B-2) is the alcohol-soluble urethane resin (A) and the It is preferably 55% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 92% by mass or less, and more preferably 65% by mass or more and 92% by mass with respect to the total mass of the hydrolyzable group-containing compound (B). % Is more preferable, and 70% by mass or more and 90% by mass or less is more preferable in forming a cured product having extremely high hardness and excellent scratch resistance. There.

  The mass of the alcohol-soluble urethane resin (A) and one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the metal alkoxide (B-1) and its condensate (B-2) The ratio can be appropriately adjusted within a range where the ratio of the total mass of the silicon atom and the oxygen atom is 50% by mass or more and 95% by mass or less. Specifically, the mass ratio of the hydrolyzable group-containing compound (B) to the total mass of the alcohol-soluble urethane resin (A) and the hydrolyzable group-containing compound (B) is 50% by mass. It is preferably used in the range of 95% by mass or less, more preferably in the range of 60% by mass or more and 95% by mass or less, and particularly preferably in the range of 65% by mass or more and 95% by mass or less.

First, the alcohol-soluble urethane resin (A) used in the present invention will be described.
The alcohol-soluble urethane resin (A) used in the present invention has an oxyethylene structure and a hydrolyzable silyl group.

The oxyethylene structure is, for example, a structure represented by the following general formula (1) that can be introduced into a molecule, a molecular end, a molecular side chain, or the like of the alcohol-soluble urethane resin (A).

(In the general formula (1), n represents an integer of 1 or more.)
Even if the said oxyethylene structure is a case where a lot of said hydrolysable group containing compounds (B) are mixed with said alcohol soluble type urethane resin (A) and alcohol (C), the urethane resin composition of this invention It is important for obtaining a cured product such as a film or a molded product having extremely high hardness and excellent scratch resistance without causing deterioration in storage stability of the product, film forming property, molding processability, and the like. Specifically, a silicon atom and an oxygen atom constituting the hydrolyzable silyl group of the alcohol-soluble urethane resin (A), and a metal atom and an oxygen atom of the hydrolyzable group-containing compound (B) It is important to make the total mass of 50% by mass or more based on the total mass of the alcohol-soluble urethane resin (A) and the hydrolyzable group-containing compound (B).

  Here, instead of the urethane resin (A), when a urethane resin having no oxyethylene structure is used, the storage stability of the urethane resin composition, the film forming property and the molding processability, In some cases, it is impossible to obtain a cured product such as a film or a molded product having extremely high hardness and excellent scratch resistance.

  In addition, by using a large amount of a strong solvent such as methyl ethyl ketone together with the alcohol (C), the solubility in a solvent such as a urethane resin having no oxyethylene structure tends to be slightly improved. However, the large amount of the hydrolyzable group-containing compound (B) still cannot exist stably and may cause the generation of aggregates. Moreover, it is not preferable to use the strong solvent from the viewpoint of reducing the environmental load.

  The oxyethylene structure is present in the range of 5 to 70% by mass with respect to the total amount of the alcohol-soluble urethane resin (A), so that the urethane resin composition has good storage stability, film-forming property, and molding. It is preferable for obtaining a cured product such as a film or a molded product that maintains workability and has extremely high hardness and excellent scratch resistance. Moreover, it is preferable that n in the said General formula (1) is an integer of 1-50, and it is more preferable that it is an integer of 10-50.

  Moreover, the hydrolyzable silyl group which the said alcohol soluble type urethane resin (A) has is 1 type chosen from the group which consists of the said metal alkoxide (B-1) and its condensate (B-2) as above-mentioned. This is important in forming a cured product such as a film or a molded product that undergoes a crosslinking reaction with the hydrolyzable group-containing compound (B) and has extremely high hardness and excellent scratch resistance.

  The hydrolyzable silyl group of the alcohol-soluble urethane resin (A) is a functional group in which the hydrolyzable group is directly bonded to a silicon atom. For example, the functional group represented by the following general formula (2) Is mentioned.

(In the general formula (2), R ¹ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, R ² is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, An amino group, an amide group, an aminooxy group, an iminooxy group or an alkenyloxy group, and x is an integer of 0 to 2.)

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, hexyl, and isohexyl groups. It is done.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group. Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

  Examples of the acyloxy group include acetoxy, propanoyloxy, butanoyloxy, phenylacetoxy, acetoacetoxy, and the like. Examples of the aryloxy group include phenyloxy, naphthyloxy, and the like. Examples of the group include an allyloxy group, a 1-propenyloxy group, and an isopropenyloxy group.

R ² is preferably independently an alkoxy group, since it is easy to remove a leaving component such as the general formula R ² OH that can be generated by hydrolysis.

  In addition, the alcohol-soluble urethane resin (A) is usually difficult to hydrolyze in the presence of the alcohol (C), so it is difficult to form a silanol group and has a hydrolyzable silyl group such as an alkoxysilyl group. A small part of them may be present in the urethane resin (A) in a silanol group state.

  The hydrolyzable silyl group may be present at either the molecular end of the alcohol-soluble urethane resin (A) or the side chain of the urethane resin (A). Among them, the use of a hydrolyzable silyl group that is present in the side chain of the molecule composed of the urethane resin (A) makes it possible to obtain a film or molded article that has higher hardness and excellent scratch resistance. It is preferable when forming hardened | cured material.

  The hydrolyzable silyl group is present in a range of 0.5 to 20% by mass with respect to the mass of the alcohol-soluble urethane resin (A), thereby improving the hardness of the resulting cured product in each stage. In addition, it is preferable for imparting excellent scratch resistance, and more preferably in the range of 0.5 to 10% by mass.

  As the alcohol-soluble urethane resin (A), it is preferable to use a resin having a number average molecular weight in the range of 5,000 to 300,000 from the viewpoint of improving ease of dissolution in the alcohol (C) described later. The range of 8000-200000 is more preferable, and the range of 100,000-200000 is particularly preferable.

  Moreover, when using what has an aromatic cyclic structure as polyisocyanate (a1) mentioned later used for manufacture of the said alcohol soluble type urethane resin (A), as said alcohol soluble type urethane resin, In order to maintain good solubility in alcohol (C), a relatively low molecular weight in the range of about 5,000 to 30,000, preferably 5,000 to 10,000 is preferable.

  The alcohol-soluble urethane resin (A) includes, for example, a urethane prepolymer (a3) having a hydroxyl group or an isocyanate group at a molecular end obtained by reacting a polyisocyanate (a1) and a polyol (a2), and an amino group. Produced by reacting at least one silane coupling agent (a4) selected from the group consisting of a containing silane coupling agent and an isocyanate group-containing silane coupling agent with a chain extender (a5) as necessary. be able to.

  Specifically, the alcohol-soluble urethane resin (A) includes a step of producing a urethane prepolymer (a3) having a hydroxyl group or an isocyanate group at a molecular end (first step), and the urethane prepolymer (a3). ) And the silane coupling agent (a4) and, if necessary, the chain extender (a5), a process for producing an alcohol-soluble urethane resin (A) that can be dissolved in the alcohol (C) (Second step).

First, the first step will be described.
The first step is a step of producing a urethane prepolymer (a3) having a hydroxyl group or an isocyanate group at the molecular end by reacting the polyisocyanate (a1) and the polyol (a2) in the absence of a solvent. .

  Here, it is important that the reaction between the polyisocyanate (a1) and the polyol (a2) is performed in the absence of a solvent. For example, when the above reaction is performed in the presence of a strong solvent such as dimethylformamide, the strong solvent often remains in the urethane resin composition, and the remaining strong solvent causes dissolution or discoloration of various substrate surfaces, In some cases, the hardness or scratch resistance of the film formed on the surface may be lowered. Moreover, when alcohol (C) mentioned later is used as a solvent, reaction of the said polyisocyanate (a1) and alcohol (C) is induced, and a desired alcohol-soluble urethane resin (A) cannot be obtained. There is a case.

  Therefore, when the reaction between the polyisocyanate (a1) and the polyol (a2) is carried out in the absence of a solvent as described above or in the presence of a solvent, a weak solvent is used or a residual solvent is sufficiently used. It is preferable to remove it.

  Reaction of the said polyisocyanate (a1) and the said polyol (a2) is equivalent ratio of the isocyanate group which the said polyisocyanate (a1) has, and the hydroxyl group which the said polyol (a2) has [isocyanate group which the polyisocyanate (a1) has / Hydroxyl group possessed by polyol (a2)] is preferably in the range of 0.8 to 10.0, more preferably in the range of 1.0 to 5.0, and in the range of 1.1 to 2.0. It is particularly preferable to carry out at

  The reaction when the polyisocyanate (a1) and the polyol (a2) are reacted in the absence of a solvent is preferably in the range of 50 ° C to 120 ° C. Preferably, at a reaction temperature of 80 ° C. to 100 ° C., the polyisocyanate (a1) and the polyol (a2) are sequentially mixed, or one of them is sequentially supplied to the other by a method such as dropping to about 1 to The reaction can be carried out for about 15 hours.

Next, the second step will be described.
The second step is a step comprising any one of the following (Method 1) to (Method 3), which is carried out following the first step of producing the urethane prepolymer (a3). This step comprises reacting the urethane prepolymer (a3), the coupling agent (a4), and, if necessary, a chain extender (a5), thereby producing an alcohol-soluble urethane having a hydrolyzable silyl group. This is a process for producing an alcohol (C) solution of resin (A).

First, the (Method 1) will be described.
The (Method 1) is a reaction in which the coupling agent (a4), the alcohol (C), and the chain extender (a5) as necessary are mixed with the urethane prepolymer (a3). This is a method for producing an alcohol (C) solution of an alcohol-soluble urethane resin (A) having a hydrolyzable silyl group.

  Specifically, a mixture containing the coupling agent (a4) and alcohol (C) prepared in advance, and, if necessary, the chain extender (a5), and the urethane prepolymer obtained in the first step. Polymer (a3) is mixed and the urethane prepolymer (a3) has an isocyanate group or a hydroxyl group, and the coupling agent (a4) or the chain extender (a5) has a functional group such as an amino group or an isocyanate group. By reacting, an alcohol (C) solution of the urethane resin (A) having a hydrolyzable silyl group introduced into the molecule can be produced.

  Here, when a monoamine silane coupling agent or a monoisocyanate group-containing silane coupling agent as described later is used as the coupling agent (a4), the hydrolyzable silyl group is obtained as an alcohol-soluble type. It introduce | transduces into the molecular terminal of a urethane resin (A). Moreover, when the diamine silane coupling agent mentioned later, a diisocyanate group containing silane coupling agent, etc. are used as the said coupling agent (a4), the said hydrolyzable silyl group is an alcohol-soluble urethane resin (A ) Introduced in the molecular side chain.

  The mixture containing the coupling agent (a4), the alcohol (C) and, if necessary, the chain extender (a5) is composed of the coupling agent (a4), the alcohol (C), and if necessary, the chain. The extender (a5) can be obtained by collectively supplying at a normal temperature, specifically, at a temperature of about 10 to 50 ° C., or sequentially supplying any of them, and mixing and stirring. Here, since the coupling agent (a4) is in the presence of the alcohol (C), it does not substantially cause a hydrolysis condensation reaction between hydrolyzable silyl groups of the coupling agent (a4). .

Next, the (Method 2) will be described.
In the (Method 2), a mixture containing the coupling agent (a4) and, if necessary, the chain extender (a5), and the urethane prepolymer (a3) are mixed and reacted. The alcohol-soluble urethane resin (A) having a hydrolyzable silyl group is prepared, and then the alcohol-soluble urethane resin (A) and the alcohol (C) are mixed to form a hydrolyzable silyl group. This is a method for producing an alcohol (C) solution of an alcohol-soluble urethane resin (A).

  Specifically, the urethane prepared in the first step, and the coupling agent (a4) alone or a mixture containing the coupling agent (a4) and the chain extender (a5) prepared in advance. The prepolymer (a3) is mixed, the isocyanate group or hydroxyl group of the urethane prepolymer (a3), and the functional group such as amino group or isocyanate group of the coupling agent (a4) or chain extender (a5). To produce the alcohol-soluble urethane resin (A) in which hydrolyzable silyl groups and / or silanol groups are introduced into the molecule.

  Next, the alcohol-soluble urethane resin (A) and the alcohol (C) thus obtained are mixed and stirred, whereby the alcohol-soluble urethane resin (A) solution of the alcohol-soluble urethane resin (A) can be obtained. . At that time, most of the silanol groups present in the urethane resin (A) form hydrolyzable silyl groups such as alkoxysilyl groups in the presence of the alcohol (C).

  When the chain extender (a5) is used together with the coupling agent (a4), the coupling agent (a4) and the chain extender (a5) are used at room temperature, specifically about 10 to 50 ° C. It is preferred to mix under conditions.

  In addition, the coupling agent (a4) alone or a mixture containing the coupling agent (a4) and the grassland extender (a5) and the urethane prepolymer (a3) is preferably 10-50. The reaction can be performed at a temperature of 10 ° C, more preferably 10 to 30 ° C.

  In addition, the mixture of the coupling agent (a4) and the chain extender (a5) and the urethane prepolymer (a3) may be mixed in a batch, or one of them may be dropped onto the other. May be carried out by a method of sequentially feeding and mixing.

  The mixing of the alcohol-soluble urethane resin (A) and the alcohol (C) obtained by the above method is preferably performed under a temperature condition of 10 to 50 ° C. Mixing of the alcohol-soluble urethane resin (A) and the alcohol (C) can also be performed by a method of mixing them all at once or by a method of sequentially supplying and mixing one of them to the other by dropping or the like. it can.

Next, (Method 3) will be described.
The (Method 3) includes a mixture of the urethane prepolymer (a3) and the alcohol (C) obtained in the first step, the coupling agent (a4), and, if necessary, a chain extender (a5). It is a method for producing an alcohol (C) solution of an alcohol-soluble urethane resin (A) having a hydrolyzable silyl group by mixing and reacting.

  Specifically, a mixture prepared by dissolving the urethane prepolymer (a3) obtained in the first step in alcohol (C) is prepared in advance, and the mixture, the coupling agent (a4), and as necessary. The chain extender (a5) is mixed, and the functional group such as an amino group or isocyanate group that the coupling agent (a4) or chain extender (a5) has, and the isocyanate group that the urethane prepolymer (a3) has. The alcohol (C) solution of the alcohol-soluble urethane resin (A) can be obtained by reacting with a hydroxyl group.

  Here, the mixing of the urethane prepolymer (a3) and the alcohol (C) is from the viewpoint of preventing the reaction between the isocyanate group of the urethane prepolymer (a3) and the hydroxyl group of the alcohol (C). It is important to carry out the reaction at room temperature or relatively low temperature, preferably 10 to 50 ° C., more preferably 10 to 30 ° C.

  The urethane prepolymer (a3) and the alcohol (C) may be mixed by a method of mixing them all together or a method of sequentially supplying one of them to the other by dropping or the like and mixing them.

  Moreover, the mixture of the urethane prepolymer (a3) and the alcohol (C), the coupling agent (a4) and, if necessary, the chain extender (a5) are mixed and stirred together. Even if it is a method to do, you may carry out by supplying one component to another component sequentially by methods, such as dripping. However, a mixture of the urethane prepolymer (a3) and the alcohol (C) was produced from the viewpoint of preventing the reaction between the isocyanate group of the urethane prepolymer (a3) and the hydroxyl group of the alcohol (C). Thereafter, the mixture is mixed with the coupling agent (a4) and the chain extender (a5) as soon as possible, specifically, preferably at a temperature of 10 to 50 ° C. within about 2 hours after the production of the mixture. Thereafter, the reaction is preferably carried out at about 10 to 50 ° C.

  The alcohol-soluble urethane resin (A) obtained by the first step and the second step has excellent solubility in the alcohol (C) described later. The solubility of the urethane resin (A) indicates that preferably 95% by mass or more of the urethane resin (A) can be dissolved in the alcohol (C), more preferably 99% by mass or more can be dissolved, and particularly preferable. Means that substantially 100% by mass is dissolved. Moreover, the solubility of the said urethane resin (A) points out the state which does not cause white turbidity when the urethane resin composition of this invention is visually observed but can maintain a transparent state.

  Examples of the polyisocyanate (a1) that can be used for the production of the alcohol-soluble urethane resin (A) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidization. Aromatic cyclic structure-containing polyisocyanates such as diphenylmethane polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, water Polyisocyanates containing aliphatic cyclic structures such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, die Over acid diisocyanate, an aliphatic polyisocyanate such as norbornene diisocyanate can be used.

  Among them, from the viewpoint of producing an alcohol-soluble urethane resin (A) that has good solubility in the alcohol (C) described later and that hardly reacts with the alcohol (C), the aliphatic cyclic It is preferable to use structure-containing polyisocyanates and aliphatic polyisocyanates, and it is particularly preferable to use isophorone diisocyanate. In addition, when using aromatic cyclic structure containing polyisocyanate alone as said polyisocyanate (a1), it is preferable to perform the said method 2 as a 2nd process at the time of manufacturing a urethane resin (A).

  As the polyol (a2) capable of reacting with the polyisocyanate (a1), an oxyethylene structure-containing polyol (a2-1) is used from the viewpoint of introducing an oxyethylene structure into the alcohol-soluble urethane resin (A). It is preferable to do.

  As said oxyethylene structure containing polyol (a2-1), what has an oxyethylene structure in a molecule | numerator or a side chain, for example can be used, for example, an oxypropylene structure and polyoxyethylene glycol, an oxyethylene structure, Random copolymers and block copolymers having both structures with other oxyalkylene structures such as a tetramethylene oxide structure can be used.

  The mass ratio of the oxyethylene structure and the other oxyalkylene structure [oxyethylene structure / other oxyalkylene structure] is necessary when forming the hydrolyzable group-containing compound (B) or a cured product. From the viewpoints of improving the compatibility with water and acid catalysts that can be used, and improving the water resistance of the resulting cured product, the mass ratio is preferably 30/70 to 60/40.

  Moreover, as said oxyethylene structure containing polyol (a2-1), what has 1 or 2 or more of hydroxyl groups in the one end of the polyoxyalkylene chain which has an oxyethylene structure can also be used. As the polyoxyalkylene chain having an oxyethylene structure having one hydroxyl group at one end, for example, polyethylene glycol monomethyl ether can be used. In addition, specifically, Ymer N120 (manufactured by Perstorp) or the like can be used as one having two or more hydroxyl groups at one end of a polyoxyalkylene chain having an oxyethylene structure.

  As the oxyethylene structure-containing polyol (a2-1), it is preferable to use an oxyethylene structure-containing polyether polyol, and a polyether polyol composed of a copolymer of ethylene oxide and tetrahydrofuran, and It is more preferable to use one or more selected from the group consisting of polyoxyethylene polyols.

  The oxyethylene structure-containing polyether polyol is produced, for example, by addition polymerization of an initiator composed of a compound having two or more active hydrogen atoms with ethylene oxide as necessary, and with other alkylene oxide as necessary. Can do. Specifically, for example, it is produced by collectively supplying alkylene oxides containing ethylene oxide or the like separately in the presence of a catalyst such as boron trifluoride and the initiator, or separately supplying, mixing and reacting each other. Can do.

  Examples of the initiator used for the production of the oxyethylene structure-containing polyether polyol include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, glycerin, and trimethylol. Propane, trimethylolethane, hexanetriol, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like can be used.

  Further, as the alkylene oxide that can react with the initiator, ethylene oxide is essential, and propylene oxide, butylene oxide, styrene oxide, γ-chloropropylene oxide (epichlorohydrin), tetramethylene oxide (tetrahydrofuran), etc., as necessary. Other alkylene oxides can be used in combination.

  The oxyethylene structure-containing polyol (a2-1) has a number average of 800 to 5000 in order to improve the compatibility with the hydrolyzable group-containing compound (B), acid catalyst such as water and maleic acid, and the like. It is preferable to use one having a molecular weight.

  The oxyethylene structure-containing polyol (a2-1) is preferably used in a range of 10 to 100% by mass, preferably 20 to 100% by mass, and 80 to 100% by mass with respect to the total amount of the polyol (a2). Is preferably used for obtaining a cured product having excellent storage stability, film-forming property, moldability, and extremely high hardness and excellent scratch resistance. .

  As said polyol (a2), another polyol can be used in combination with the said oxyethylene structure containing polyol (a2-1) as needed.

  Examples of the other polyols include polyols having no oxyethylene structure, such as polyether polyols, polyester polyols, and polycarbonate polyols having no oxyethylene structure. When improving the solvent resistance etc. of the cured | curing material obtained, it is preferable to use polyester polyol and polycarbonate polyol as said other polyol.

  As said other polyether polyol, what was obtained by carrying out addition polymerization of the above-mentioned initiator and alkylene oxide which do not have an oxyethylene structure, for example can be used.

  As said polyether polyol, polyoxytetramethylene glycol, polyoxypropylene glycol, etc. can be used, for example.

  Examples of the other polyester polyols include aliphatic polyester polyols and aromatic polyester polyols obtained by esterifying low molecular weight polyols and polycarboxylic acids, and cyclic ester compounds such as ε-caprolactone and γ-butyrolactone. Polyester obtained by ring-opening polymerization reaction, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1, 4-Cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more.

  Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and these. An anhydride or an ester-forming derivative can be used. In addition, when using the said aromatic cyclic structure containing polyester polyol, it is preferable to use aromatic polycarboxylic acids, such as a terephthalic acid, isophthalic acid, a phthalic acid, and a naphthalene dicarboxylic acid, as the said polycarboxylic acid.

  Moreover, as said other polycarbonate polyol, what is obtained by making carbonate ester and a polyol react, for example, what is obtained by making phosgene, bisphenol A, etc. react can be used.

  As the carbonate ester, 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 include 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,2-butanediol. 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2-butyl-2- Tylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4 ′ -Relatively low molecular weight dihydroxy compounds such as biphenols can be used.

  As the polyol (a2), in addition to those described above, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6- Relatively low molecular weight polyols such as hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, dipropylene glycol, glycerin, trimethylolpropane and dimethylolpropionic acid can also be used.

  As said other polyol, it is preferable to use what has the number average molecular weight of the range of 800-5000, and it is more preferable to use the thing of the range of 800-3000.

  The coupling agent (a4) used for the production of the alcohol-soluble urethane resin (A) is used for introducing a hydrolyzable silyl group into the molecular terminal or molecular side chain of the urethane resin (A).

  As said coupling agent (a4), an amino group containing silane coupling agent and an isocyanate group containing silane coupling agent can be used, for example.

  As said amino group containing silane coupling agent, a monoamine silane coupling agent and a diamine silane coupling agent can be used, for example. In the monoamine silane coupling agent, when the molecular end of the urethane prepolymer (a3) is an isocyanate group, the isocyanate group reacts with the amino group of the monoamine silane coupling agent. Thereby, the alcohol-soluble urethane resin (A) having a hydrolyzable silyl group at the molecular end can be obtained.

  On the other hand, when the molecular end of the urethane prepolymer (a3) is an isocyanate group, the isocyanate group reacts with the amino group of the diamine silane coupling agent. Thereby, it is possible to obtain an alcohol-soluble urethane resin (A) having a hydrolyzable silyl group in the molecular side chain instead of the molecular end.

  Examples of the monoamine silane coupling agent include monoamine silane coupling agents such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane. Can be used alone or in combination of two or more.

  As the diamine silane coupling agent, for example, a diamine silane coupling agent such as N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane alone or Two or more types can be used in combination.

  Moreover, as said isocyanate group containing silane coupling agent, a monoisocyanate group containing silane coupling agent and a diisocyanate group containing silane coupling agent can be used, for example.

  In the monoisocyanate group-containing silane coupling agent, when the molecular end of the urethane prepolymer (a3) is a hydroxyl group, the hydroxyl group reacts with the isocyanate group of the monoisocyanate group-containing silane coupling agent. Thereby, the alcohol-soluble urethane resin (A) having a hydrolyzable silyl group at the molecular end can be obtained.

  On the other hand, in the diisocyanate group-containing silane coupling agent, when the molecular end of the urethane prepolymer (a3) is a hydroxyl group, the hydroxyl group reacts with the isocyanate group of the diisocyanate group-containing silane coupling agent. Thereby, it is possible to obtain an alcohol-soluble urethane resin (A) having a hydrolyzable silyl group in the molecular side chain instead of the molecular end.

  As said monoisocyanate group containing silane coupling agent, (gamma) -isocyanate propyl triethoxysilane, (gamma) -isocyanate propyl trimethoxysilane etc. can be used individually or in combination of 2 or more types, for example.

  As the coupling agent (a4), a hydrolyzable silyl group is introduced into a side chain of a molecule composed of the alcohol-soluble urethane resin (A), and a cured product having even better scratch resistance is obtained. In obtaining, it is preferable to use a diamine silane coupling agent or a diisocyanate group-containing silane coupling agent, and more preferably to use a diamine silane coupling agent.

  The coupling agent (a4) is used in a range where the amino group has a ratio of 0.01 to 1.0 (equivalent ratio) with respect to 1.00 equivalent of the isocyanate group of the urethane prepolymer (a3). It is preferable to use it at a ratio of 0.01 to 0.9 (equivalent ratio). Moreover, when a functional group is a hydroxyl group at the molecular terminal of the urethane prepolymer (a3), the isocyanate group of the coupling agent (a4) is 0.01 to 1 with respect to 1.00 equivalent of the hydroxyl group. It is preferable to use in the range which becomes the ratio of 0 (equivalent ratio), and it is more preferable to use it in the ratio of 0.01-0.9 (equivalent ratio).

  When the alcohol-soluble urethane resin (A) is produced, the urethane resin (A) has a high molecular weight, and the obtained cured product is imparted with extremely high hardness and particularly excellent scratch resistance. The chain extender (a5) can be used as necessary.

  Since the diamine silane coupling agent or diisocyanate group-containing silane coupling agent as the coupling agent (a4) can be used as a chain extender, the chain extender is used when they are used. (A5) is not necessarily used.

  However, when the monoamine silane coupling agent or the monoisocyanate group-containing silane coupling agent is used as the coupling agent (a4), for example, the alcohol-soluble urethane resin (A) has a high molecular weight and is extremely high. The chain extender (a5) is preferably used in order to obtain a cured product having particularly excellent scratch resistance in hardness.

  As the chain extender (a5), conventionally known amine compounds and alkanolamines can be used. Of these, diamines are preferably used.

  Examples of the diamine include dicyclohexylmethanediamine, isophoronediamine, 4,4′-diphenylmethanediamine, diaminoethane, 1,2- or 1,3-diaminopropane, 1,2- or 1,3- or 1,4- Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N′-bis- (2-aminoethyl) piperazine, bis- (4-aminocyclohexyl) methane, bis- (4-amino) -3-Butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, hydrazine, dihydrazine adipate and the like can be used alone or in combination of two or more. Among these, from the viewpoint of producing the alcohol-soluble urethane resin (A) excellent in solubility in the alcohol (C), it is preferable to use an aliphatic cyclic structure-containing diamine or an aliphatic diamine, and dicyclohexylmethane. More preferably, diamine or isophoronediamine is used.

  In the present invention, in addition to the diamine, other chain extenders may be used in combination as necessary. For example, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3′-dimethylol heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3 , 3-bis (hydroxymethyl) heptane, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, glycerin, trimethylolpropane, sorbitol, hydroquinone diethylol ether, and the like can also be used.

  The diamine is preferably used in a range where the amino group has a ratio of 0.50 to 1.00 (equivalent ratio) with respect to 1.00 equivalent of the isocyanate group of the urethane prepolymer (a3). It is more preferable to use at a ratio of .60 to 0.90 in order to impart excellent heat resistance to the obtained cured product.

  When a monoamine silane coupling agent or a diamine silane coupling agent is used as the coupling agent (a4) and a diamine as the chain extender (a5) is used in combination, a urethane prepolymer (a3 In the range where the amino group of the coupling agent (a4) and the chain extender (a5) is in a ratio of 0.50 to 1.00 (equivalent ratio) with respect to 1.00 equivalent of the isocyanate group of It is preferable to use it, and it is more preferable to use it in the ratio of 0.60-0.90, when giving the outstanding heat resistance to the hardened | cured material obtained.

  The alcohol-soluble urethane resin (A) obtained by the above method is based on the total mass of the alcohol-soluble urethane resin (A), the hydrolyzable group-containing compound (B), and the alcohol (C). In order to form a cured product having extremely high hardness and excellent scratch resistance, etc., it is preferable to use in the range of 3% by mass to 20% by mass. Is preferable.

  Next, at least one hydrolyzable group-containing compound (B) selected from the group consisting of the metal alkoxide (B-1) and its condensate (B-2) used in the present invention will be described.

  The metal alkoxide (B-1) is a compound in which an alkoxy group is bonded to a metal atom. Specifically, as the metal alkoxide (B-1), one having a structure represented by the following general formula (3) can be used.

M (OR) n (3)
(M in the general formula (3) represents a metal atom, R represents an alkyl group, and n represents an integer in the range of 1 to the valence of the metal atom M.)
Examples of M include a silicon atom, a titanium atom, an aluminum atom, a magnesium atom, a germanium atom, a lithium atom, and a sodium atom. Moreover, as said R, a C1-C10 alkyl group is mentioned, Specifically, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.

  In addition, the metal alkoxide condensate (B-2) refers to a product in which a part of the alkoxy group of the metal alkoxide is hydrolyzed to form a hydroxyl group and subjected to a condensation reaction with another alkoxy group or a hydroxyl group.

  The metal constituting the one or more hydrolyzable group-containing compound (B) selected from the group consisting of the metal alkoxide (B-1) and its condensate (B-2) (M in the general formula (I) ) Include, for example, silicon atom, titanium atom, aluminum atom and the like. Among them, the use of a metal alkoxide in which the metal is a silicon atom or a condensate thereof is industrially easily available, and the urethane resin (A) has a hydrolyzable silyl group or silanol group and a crosslinking reaction. However, it is preferable for forming a film having extremely high hardness and excellent scratch resistance.

  As the metal alkoxide (B-1) in which the metal is a silicon atom and the condensate (B-2) thereof, a hydrolyzable silyl group-containing compound generally used in a sol-gel reaction can be used.

  Examples of the hydrolyzable silyl group-containing compound include alkoxysilyl group-containing compounds, such as tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, Methoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methyl Trialkoxysilanes such as captopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane Alkoxy silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane, or partial condensates thereof can be used.

  Among these, it is preferable to use tetramethoxysilane or a partially hydrolyzed condensate thereof because a cured product having an extremely high hardness and excellent scratch resistance can be formed by promptly proceeding with a crosslinking reaction.

  In addition, as the metal alkoxide in which the metal is a titanium atom or a condensate thereof, for example, titanium alkoxide such as titanium isopropoxide, titanium lactate, titanium triethanolamate, and the like can be used.

  Moreover, as a metal alkoxide whose metal is an aluminum atom, or its condensate, aluminum alkoxides, such as aluminum isopropoxide, can be used, for example.

Next, the alcohol (C) used in the present invention will be described.
The alcohol (C) is used as a solvent for the alcohol-soluble urethane resin (A) and the hydrolyzable group-containing compound (B).

  The alcohol (C) may have any structure such as a straight chain structure, a branched structure, and a cyclic structure, but from the viewpoint of enhancing the ease of dissolution of the urethane resin (A), methyl alcohol, ethyl alcohol, It is preferable to use an alcohol having 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms, such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, It is more preferable to use methyl alcohol, ethyl alcohol, n-propyl alcohol, or isopropyl alcohol alone or in combination of two or more.

  Unlike the strong solvent such as DMF, the alcohol (C) is classified as a weak solvent. For example, when the urethane resin composition of the present invention is applied to the surface of an adherend, However, it does not cause dissolution or deterioration of the adherend surface. In particular, when the adherend is a porous body, the pores constituting the porous body are not broken, and the flexibility derived from the porous body is not impaired.

  One or more hydrolysiss selected from the group consisting of the hydrolyzable silyl group of the alcohol-soluble urethane resin (A), the metal alkoxide (B-1), and the condensate (B-2) thereof. The hydrolysis-condensation reaction does not substantially proceed with the alkoxy group bonded to the metal atom constituting the functional group-containing compound (B) in the presence of an excessive amount of alcohol (C). Therefore, in the urethane resin composition of the present invention, it is important to use the alcohol (C) as a solvent in order to maintain excellent storage stability.

  The alcohol (C) is used in a range of 20 to 70% by mass with respect to the total mass of the alcohol-soluble urethane resin (A), the hydrolyzable group-containing compound (B), and the alcohol (C). It is more preferable to maintain even better storage stability.

  In addition, the urethane resin composition of this invention contains other solvents other than the said alcohol (C) as solvents, such as the said alcohol soluble type urethane resin (A) and the said hydrolysable group containing compound (B). It may be. For example, it does not exclude the presence of a strong solvent such as dimethylformamide or toluene, but the amount used is preferably as small as possible from the viewpoint of reducing environmental burden. Specifically, in the urethane resin composition of the present invention, the mass ratio of the alcohol (C) to the total mass of the solvent contained in the composition is preferably 95 to 100% by mass, and 98 to 100. More preferably, it is 100 mass%, and it is especially preferable that it is 100 mass%.

  The urethane resin composition of the present invention is, for example, 1 selected from the group consisting of the alcohol-soluble urethane resin (A) obtained by the above method, the metal alkoxide (B-1) and the condensate (B-2) thereof. It can manufacture by mixing a hydrolysable group containing compound (B) of a seed or more and alcohol (C).

  Specifically, it is selected from the group consisting of an alcohol (C) solution of an alcohol-soluble urethane resin (A) produced in advance by the above method, the metal alkoxide (B-1) and a condensate (B-2) thereof. One or more hydrolyzable group-containing compounds (B) can be supplied all at once, or one can be sequentially supplied to the other and mixed and stirred. The hydrolyzable group-containing compound (B) may be previously mixed with an alcohol (C) or the like, and is produced by hydrolysis of a part of the hydrolyzable group-containing compound (B). It may contain alcohol. The alcohol produced by the hydrolysis may be removed by a method such as standing or heating under reduced pressure as necessary.

  One or more hydrolyzable group-containing compounds (B) selected from the group consisting of an alcohol (C) solution of the urethane resin (A), the metal alkoxide (B-1) and a condensate (B-2) thereof. The mixing with can be performed, for example, using a stirring rod or the like under a temperature condition of about 10 to 50 ° C., or using a stirring device such as a homomixer. As the mixing method, it is preferable to use a stirring device such as a homomixer from the viewpoint of uniformly dispersing the inorganic particles (B).

  In the urethane resin composition of the present invention, if necessary, for example, an acid catalyst, a crosslinking agent, a film forming aid, a filler, a thixotropic agent, a tackifier, a surfactant, a pigment, a resin for blending, Other additives and the like can be added as long as the object of the present invention is not impaired.

  The acid catalyst is preferably used for the purpose of promptly proceeding with the curing of the urethane resin composition of the present invention. Specifically, before applying the urethane resin composition of the present invention to the surface of a substrate or the like, the urethane resin composition obtained by mixing the urethane resin composition, the acid catalyst and water, A composition containing the acid catalyst and the water is applied to the surface of a substrate or the like. Thereby, the hydrolyzable silyl group of the urethane resin (A) in the coating layer quickly forms a silanol group, and the alkoxy group bonded to the metal atom of the hydrolyzable group-containing compound (B) also A hydroxyl group can be quickly formed, and a crosslinking reaction between the silanol group and the hydroxyl group can be rapidly advanced.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, boric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and organic acids such as acetic acid, phthalic acid, maleic acid, fumaric acid, and paratoluenesulfonic acid. More than one species can be used in combination. Among these, maleic acid or phosphoric acid is preferably used because a cured product such as a film having extremely high hardness and excellent scratch resistance can be formed quickly.

  The acid catalyst is preferably used in a range of 1 to 50 parts by weight, and in a range of 2 to 40 parts by weight, based on 100 parts by weight of the hydrolyzable group-containing compound (B). It is preferable for promptly proceeding with the crosslinking reaction.

  As said crosslinking agent, an isocyanate type crosslinking agent can be used, for example, specifically, tolylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, trimethylolpropane modified tolylene diisocyanate, etc. Can be used.

  The film forming aid is not particularly limited, and examples thereof include anionic surfactants (such as dioctyl sulfosuccinate soda salt), hydrophobic nonionic surfactants (such as sorbitan monooleate), and silicone oil. It is done.

  Examples of the filler include metal oxides such as silicon, aluminum, titanium, zirconium, zinc, and tin and their hydrolysis condensates, carbonates (for example, calcium salts, calcium / magnesium salts, magnesium salts, etc.), Silicic acid, silicate (eg aluminum salt, magnesium salt, calcium salt etc.), hydroxide (eg aluminum salt, magnesium salt, calcium salt etc.), sulfate (eg barium salt, calcium salt, magnesium salt etc.), borate (For example, aluminum salt, zinc salt, calcium salt, etc.), titanate (for example, potassium salt, etc.) and the like.

  Examples of the thixotropy-imparting agent 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.

  Although it does not specifically limit as said tackifier, For example, tackifiers, such as a rosin resin type, a terpene resin type, a phenol resin type, are mentioned.

  Furthermore, other additives include, for example, reaction accelerators (metal-based, metal salt-based, amine-based, etc.), stabilizers (ultraviolet absorbers, antioxidants, heat-resistant stabilizers, etc.), moisture removal agents (4- And various additives such as adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion-imparting agents, antifoaming agents, and leveling agents.

  The urethane resin composition of the present invention is less likely to cause gelation and the like, and is excellent in dispersion stability and storage stability, and when cured, it can form a cured product with extremely high hardness and excellent scratch resistance. it can. Moreover, since alcohol is used as a solvent, it does not cause dissolution or deterioration of the substrate surface.

  Therefore, the urethane resin composition of the present invention can be used, for example, as a coating agent, preferably a hard coating agent, used for coating the surface of a member that requires extremely high hardness and scratch resistance.

  Examples of the base material that can be coated with the coating agent to form a film or can be bonded include a glass base material, a metal base material, a plastic base material, a paper or wood base material, and a fibrous base material. . Moreover, it can also be used for the base material of porous body structures, such as a urethane foam.

  As said metal base material, galvanized steel plates, such as a galvanized steel plate and 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 etc. can be used, for example.

  Examples of the plastic base material include polycarbonate base materials, polyester base materials, acrylonitrile-butadiene-styrene base materials, polyacryl base materials, polystyrene base materials, polyurethane base materials, epoxy resin base materials, polyvinyl chloride base materials, and the like. A polyamide-based substrate or the like can be used.

  The base material may be a planar material made of the above material or may have a curved portion, or may be a base material made of fibers such as a nonwoven fabric.

  Examples of the method for applying the coating agent or the like 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.

  Moreover, the urethane resin composition of the present invention can be used, for example, for producing a cured product having extremely high hardness and excellent scratch resistance, such as an automobile member, a household appliance part, and an electronic material.

  As a method of curing the urethane resin composition of the present invention and forming a cured product such as a film or a molded product, for example, by mixing the urethane resin composition and, if necessary, the acid catalyst and water, A composition containing the urethane resin composition, an acid catalyst, and water is obtained, the composition is applied to a substrate surface, and the alcohol (C) contained in the coating layer is removed to thereby remove the alcohol. 1 selected from the group consisting of a silanol group formed by hydrolysis of a hydrolyzable silyl group of a soluble urethane resin (A), the metal alkoxide (B-1) and a condensate (B-2) thereof. The manufacturing method of the hardened | cured material characterized by reacting the hydroxyl group produced | generated by the hydrolysis of the alkoxy group couple | bonded with the metal atom of the hydrolyzable group containing compound (B) of a seed | species or more forms a bond. It is done.

  The step of removing the alcohol (C) is preferably performed, for example, by leaving it at room temperature or leaving it at about 30 to 80 ° C.

  Moreover, the group which consists of the silanol group formed by hydrolyzing the hydrolyzable silyl group of the said alcohol soluble type urethane resin (A), the said metal alkoxide (B-1), and its condensate (B-2). The step of forming a bond by reacting a hydroxyl group produced by hydrolysis of an alkoxy group bonded to a metal atom of one or more hydrolyzable group-containing compounds (B) selected from about 80 to 150, for example. By heating to ° C., it can be rapidly advanced.

  In addition, when the hydrolysis condensation reaction is difficult by heating alone, or when the substrate is made of a material that is weak against heat, the acid catalyst and water are mixed in advance with the urethane resin composition of the present invention. By using the composition obtained in this manner, the reaction can proceed promptly.

  The water is not used as a solvent for the urethane resin composition of the present invention, but is preferably used when the crosslinking reaction proceeds. The water is preferably used in the range of 1 to 100 parts by weight, and in the range of 5 to 50 parts by weight, based on 100 parts by weight of the hydrolyzable group-containing compound (B). It is preferable for promptly proceeding the reaction.

  A cured product such as a film or a molded product obtained by such a method has an extremely high hardness and can prevent the occurrence of scratches even when it is rubbed with a metal or the like.

  As described above, coating agents and molding materials containing the urethane resin composition of the present invention include, for example, mobile phones, home appliances, OA equipment, automobile parts such as automobile interior and exterior materials, parts of various household appliances, electronic It can be used in various applications including production of materials, building material products, medical materials such as artificial bones and artificial teeth, and surface coating and adhesion thereof.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Synthesis Example 1] Preparation of alcohol solution of alcohol-soluble urethane resin (A-1) In a nitrogen-substituted reaction vessel equipped with a stirrer, 47 parts by mass of isophorone diisocyanate, polyethylene oxide, poly A polyether polyol composed of a block copolymer with a tetramethylene oxide structure (number average molecular weight 1800, [polyoxyethylene structure / polytetramethylene oxide structure] = 45/55) is mixed with 153 parts by mass, and 3 parts at 80 ° C. are mixed. By reacting for a period of time, a urethane prepolymer (x-1) having an isocyanate group at the molecular end was produced.

  Next, the reaction vessel was cooled until the temperature of the urethane prepolymer (x-1) reached 40 ° C., and then the urethane prepolymer (x-1) and 527 parts by mass of isopropyl alcohol were mixed. 4.25 parts by mass of β- (aminoethyl) -γ-aminopropyltriethoxysilane were mixed and stirred for 15 minutes.

  Next, after mixing 21.8 parts by mass of dicyclohexylmethanediamine, oxymethane was added by further adding dicyclohexylmethanediamine and reacting at 40 ° C. for 3 hours until the viscosity of the mixture was in the range of 150 dPa · s to 450 dPa · s. An isopropyl alcohol solution (non-volatile content: 30% by mass) of an alcohol-soluble urethane resin (A-1) having a number average molecular weight of 180,000 having an ethylene structure and a hydrolyzable silyl group in the molecular side chain was obtained. In addition, the said number average molecular weight created the dimethylformamide solution (nonvolatile matter 0.4 mass%) of the said urethane resin (A-1), and the gel permeation chromatograph (GPC, conditions; column by polystyrene conversion) (KD-806M; manufactured by Showa Denko KK), eluent (DMF)). The following synthesis examples 2 and 3 and comparative synthesis examples 4 and 5 were also measured in the same manner.

[Synthesis Example 2] Preparation of alcohol solution of alcohol-soluble urethane resin (A-2) In a nitrogen-substituted reaction vessel equipped with a stirrer, 47 parts by mass of isophorone diisocyanate, polyethylene oxide, poly A polyether polyol composed of a block copolymer with a tetramethylene oxide structure (number average molecular weight 1800, [polyoxyethylene structure / polytetramethylene oxide structure] = 45/55) is mixed with 153 parts by mass, and 3 parts at 80 ° C. are mixed. By reacting for a period of time, a urethane prepolymer (x-1) having an isocyanate group at the molecular end was produced.

  Next, the reaction vessel was cooled until the temperature of the urethane prepolymer (x-1) reached 40 ° C., and then the urethane prepolymer (x-1) and 527 parts by mass of isopropyl alcohol were mixed. 1.7 parts by mass of 2- (aminoethyl) -3-aminopropyltriethoxysilane was mixed and stirred for 15 minutes.

  Next, after mixing 21.8 parts by mass of dicyclohexylmethanediamine, oxymethane was added by further adding dicyclohexylmethanediamine and reacting at 40 ° C. for 3 hours until the viscosity of the mixture was in the range of 150 dPa · s to 450 dPa · s. An isopropyl alcohol solution (non-volatile content: 30% by mass) of an alcohol-soluble urethane resin (A-2) having a number average molecular weight of 180,000 having an ethylene structure and a hydrolyzable silyl group in the molecular side chain was obtained.

[Synthesis Example 3] Preparation of alcohol solution of alcohol-soluble urethane resin (A-3) In a nitrogen-substituted reaction vessel equipped with a stirrer, 47 parts by mass of isophorone diisocyanate, polyethylene oxide, poly A polyether polyol composed of a block copolymer with a tetramethylene oxide structure (number average molecular weight 1800, [polyoxyethylene structure / polytetramethylene oxide structure] = 45/55) is mixed with 153 parts by mass, and 3 parts at 80 ° C. are mixed. By reacting for a period of time, a urethane prepolymer (x-1) having an isocyanate group at the molecular end was produced.

  Next, the reaction vessel was cooled until the temperature of the urethane prepolymer (x-1) reached 40 ° C., and the urethane prepolymer (x-1) and 527 parts by mass of isopropyl alcohol were mixed, and immediately, dicyclohexylmethane. 24 parts by mass of diamine were mixed, and further dicyclohexylmethanediamine was added and reacted until the viscosity of the obtained mixture was in the range of 150 dPa · s to 450 dPa · s, thereby obtaining a reaction mixture.

  Next, the reaction mixture and 1.7 parts by mass of γ-aminopropyltriethoxysilane are mixed and reacted at 40 ° C. for 3 hours, thereby having a number average having an oxyethylene structure and a hydrolyzable silyl group at the molecular end. An isopropyl alcohol solution (nonvolatile content: 30% by mass) of an alcohol-soluble urethane resin (A-3) having a molecular weight of 180,000 was obtained.

[Comparative Synthesis Example 4] Preparation of alcohol solution of alcohol-soluble urethane resin (A'-4) In a nitrogen-substituted reaction vessel equipped with a stirrer, 47 parts by mass of isophorone diisocyanate and polyethylene oxide in the absence of solvent. And 153 parts by mass of a polyether polyol (number average molecular weight 1800, [polyoxyethylene structure / polytetramethylene oxide structure] = 45/55) consisting of a block copolymer of a polytetramethylene oxide structure and 80 ° C. The urethane prepolymer (x-1) was produced by reacting for 3 hours under stirring.

  Next, the reaction vessel was cooled until the temperature of the urethane prepolymer (x-1) reached 40 ° C., and the urethane prepolymer (x-1) and 527 parts by mass of isopropyl alcohol were mixed, and immediately, dicyclohexylmethane. 24 parts by mass of diamine are mixed, and an alcohol having a number average molecular weight of 180,000 having an oxyethylene structure is obtained by further adding dicyclohexylmethanediamine and reacting until the viscosity of the resulting mixture is in the range of 150 dPa · s to 450 dPa · s. An isopropyl alcohol solution (nonvolatile content: 30% by mass) of a soluble urethane resin (A′-4) was obtained.

[Comparative Synthesis Example 5] Preparation of alcohol solution of alcohol-soluble urethane resin (A'-5) In a nitrogen-substituted reaction vessel equipped with a stirrer, 47 parts by mass of isophorone diisocyanate and 2- A urethane prepolymer (x-2) was produced by mixing 153 parts by mass of ethyl-2-butylpropane adipate (number average molecular weight 1800) and reacting at 80 ° C. for 3 hours with stirring.

  Next, the reaction vessel was cooled until the temperature of the urethane prepolymer (x-2) reached 40 ° C., and the urethane prepolymer (x-2) and 527 parts by mass of isopropyl alcohol were mixed, and immediately, dicyclohexylmethane. 24 parts by mass of diamine were mixed, and further dicyclohexylmethanediamine was added and reacted until the viscosity of the obtained mixture was in the range of 150 dPa · s to 450 dPa · s, thereby obtaining a reaction mixture.

  Next, the reaction mixture and 1.7 parts by mass of γ-aminopropyltriethoxysilane are mixed and reacted at 40 ° C. for 3 hours, thereby having a number average having an oxyethylene structure and a hydrolyzable silyl group at the molecular end. An isopropyl alcohol solution (non-volatile content: 30% by mass) of an alcohol-soluble urethane resin (A′-5) having a molecular weight of 180,000 was obtained.

[Example 1] <Urethane resin composition>
In the mixture, 35.0 parts by mass of an alcohol solution (non-volatile content 30% by mass) of alcohol-soluble urethane resin (A-1) obtained in Synthesis Example 1 and 35.0 parts by mass of isopropyl alcohol were stirred and mixed. 30.0 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of the SiO ₂ structure) is gradually mixed. A urethane resin composition (1) was obtained.

<Hardened product (film)>
To the urethane resin composition (1) obtained above, 21.0 parts by mass of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was further continued for 30 minutes. Thereafter, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (1). The coating agent (1) was applied on a glass plate (manufactured by Engineering Test Service Co., Ltd., JIS3202 glass, size 2.0 × 70 × 150 mm), and then dried at 110 ° C. for 5 minutes to obtain a film thickness of about A 10 μm film (1) was prepared.

[Example 2] <Urethane resin composition>
After stirring and mixing 34.8 parts by mass of an alcohol solution (non-volatile content 30% by mass) of alcohol-soluble urethane resin (A-2) obtained in Synthesis Example 2 and 34.8 parts by mass of isopropyl alcohol, 30.4 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of the SiO ₂ structure) is gradually mixed. A urethane resin composition (2) was obtained.

  To the urethane resin composition (2) obtained above, 21.3 parts by mass of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was continued for another 30 minutes. Then, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (2).

  A film (2) having a thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (2) was used instead of the coating agent (1).

[Example 3] <Urethane resin composition>
After stirring and mixing 34.8 parts by mass of the alcohol solution (non-volatile content 30% by mass) of the alcohol-soluble urethane resin (A-3) obtained in Synthesis Example 3 and 34.8 parts by mass of isopropyl alcohol, 30.4 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of the SiO ₂ structure) is gradually mixed. A urethane resin composition (3) was obtained.

  To the urethane resin composition (3) obtained above, 21.3 parts by mass of a maleic acid aqueous solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was continued for another 30 minutes. Thereafter, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (3).

  A film (3) having a thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (3) was used instead of the coating agent (1).

[Comparative Example 1] <Urethane resin composition>
After stirring and mixing 34.7 parts by mass of an alcohol solution (non-volatile content 30% by mass) of alcohol-soluble urethane resin (A′-4) obtained in Comparative Synthesis Example 4 and 34.7 parts by mass of isopropyl alcohol, Urethane resin by gradually mixing 30.6 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of SiO ₂ structure) in the mixture. A composition (1 ′) was obtained.

  To the urethane resin composition (1 ′) obtained above, 21.4 parts by mass of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was continued for another 30 minutes. Then, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (1 ′).

  A film (1 ') having a film thickness of about 10 m was prepared in the same manner as in Example 1 except that the coating agent (1') was used instead of the coating agent (1).

[Example 4] <Urethane resin composition>
After stirring and mixing 30.0 parts by mass of an alcohol solution (non-volatile content 30% by mass) of the alcohol-soluble urethane resin (A-1) obtained in Synthesis Example 1 and 30.0 parts by mass of isopropyl alcohol, 40.0 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of the SiO ₂ structure) is gradually mixed. A urethane resin composition (4) was obtained.

  To the urethane resin composition (4) obtained above, 28.0 parts by weight of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring, and stirring was continued for another 30 minutes after the addition. Thereafter, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (4).

  A film (4) having a film thickness of about 10 μm was prepared in the same manner as in Example 1 except that the coating agent (4) was used instead of the coating agent (1).

[Example 5] <Urethane resin composition>
After 29.8 parts by mass of the alcohol-soluble urethane resin (A-2) obtained in Synthesis Example 2 (non-volatile content 30% by mass) and 29.8 parts by mass of isopropyl alcohol were stirred and mixed, 40.4 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of the SiO ₂ structure) is gradually mixed. A urethane resin composition (5) was obtained.

  To the urethane resin composition (5) obtained above, 28.3 parts by mass of an aqueous maleic acid solution (non-volatile content 28.6% by mass) was gradually added with stirring, and stirring was continued for another 30 minutes after the addition. Thereafter, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (5).

  A film (5) having a thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (5) was used instead of the coating agent (1).

[Example 6] <Urethane resin composition>
After 29.8 parts by mass of the alcohol solution (non-volatile content 30% by mass) of alcohol-soluble urethane resin (A-3) obtained in Synthesis Example 3 and 29.8 parts by mass of isopropyl alcohol were stirred and mixed, 40.4 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of the SiO ₂ structure) is gradually mixed. A urethane resin composition (6) was obtained.

  To the urethane resin composition (6) obtained above, 28.3 parts by mass of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was continued for another 30 minutes. Thereafter, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (6).

  A film (6) having a thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (6) was used instead of the coating agent (1).

[Comparative Example 2] <Urethane resin composition>
29.7 parts by mass of an alcohol solution (non-volatile content 30% by mass) of alcohol-soluble urethane resin (A′-4) obtained in Comparative Synthesis Example 4 and 29.7 parts by mass of isopropyl alcohol were stirred and mixed. By gradually mixing 40.6 parts by mass of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of the SiO ₂ structure) in the mixture, urethane was obtained. A resin composition (2 ′) was obtained.

  To the urethane resin composition (2 ′) obtained above, 28.4 parts by weight of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was continued for another 30 minutes. Then, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (2 ′).

  A film (2 ') having a film thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (2 ′) was used instead of the coating agent (1).

[Example 7] <Urethane resin composition>
In the mixture, 13.9 parts by mass of an alcohol solution (non-volatile content 30% by mass) of the alcohol-soluble urethane resin (A-1) obtained in Synthesis Example 1 and 13.9 parts by mass of isopropyl alcohol were stirred and mixed. By gradually mixing 72.2 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (ratio 51% by mass occupied by SiO ₂ structure), A urethane resin composition (7) was obtained.

  To the urethane resin composition (7) obtained above, 50.5 parts by mass of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was further continued for 30 minutes. Thereafter, the resulting mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (7).

  A film (7) having a thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (7) was used instead of the coating agent (1).

[Example 8] <Urethane resin composition>
In the mixture, 13.8 parts by mass of an alcohol solution (non-volatile content: 30% by mass) of alcohol-soluble urethane resin (A-2) obtained in Synthesis Example 2 and 13.8 parts by mass of isopropyl alcohol were stirred and mixed. In addition, 72.4 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of SiO ₂ structure) is gradually mixed. A urethane resin composition (8) was obtained.

  To the urethane resin composition (8) obtained above, 50.7 parts by mass of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was further continued for 30 minutes. Thereafter, the resulting mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (8).

  A film (8) having a film thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (8) was used instead of the coating agent (1).

[Example 9] <Urethane resin composition>
In the mixture, 13.8 parts by mass of the alcohol solution (non-volatile content 30% by mass) of alcohol-soluble urethane resin (A-3) obtained in Synthesis Example 3 and 13.8 parts by mass of isopropyl alcohol were stirred and mixed. In addition, 72.4 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of SiO ₂ structure) is gradually mixed. A urethane resin composition (9) was obtained.

  To the urethane resin composition (9) obtained above, 50.7 parts by mass of a maleic acid aqueous solution (non-volatile content: 28.6% by mass) was gradually added with stirring, and stirring was continued for another 30 minutes after the addition. Thereafter, the resulting mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (9).

  A film (9) having a film thickness of about 10 μm was produced in the same manner as in Example 1 except that the coating agent (9) was used instead of the coating agent (1).

[Comparative Example 3] <Urethane resin composition>
After stirring and mixing 13.7 parts by mass of an alcohol solution (non-volatile content 30% by mass) of the alcohol-soluble urethane resin (A′-4) obtained in Comparative Synthesis Example 4 and 13.7 parts by mass of isopropyl alcohol, Urethane resin by gradually mixing 72.6 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass occupied by SiO ₂ structure) in the mixture. A composition (3 ′) was obtained.

  To the urethane resin composition (3 ′) obtained above, 50.8 parts by mass of an aqueous maleic acid solution (non-volatile content: 28.6% by mass) was gradually added with stirring. After the addition, stirring was continued for another 30 minutes. Then, the obtained mixture was filtered using a 200 mesh nylon shear to obtain a coating agent (3 ′).

  A film (3 ') having a film thickness of about 10 m was prepared in the same manner as in Example 1 except that the coating agent (3') was used instead of the coating agent (1).

[Comparative Example 4] <Urethane resin composition>
After stirring and mixing 38.0 parts by mass of an alcohol solution (non-volatile content 30% by mass) of the alcohol-soluble urethane resin (A′-5) obtained in Comparative Synthesis Example 5 and 38.0 parts by mass of isopropyl alcohol, Urethane resin by gradually mixing 24.0 parts by mass of 99% by mass of tetramethoxysilane and its partial hydrolysis-condensation product and 1% by mass of methanol (51% by mass of SiO ₂ structure) in the mixture. A composition (4 ′) was obtained.

  However, since the obtained urethane resin composition (4 ') was poor in storage stability and agglomeration of tetramethoxysilane and its partial hydrolysis condensate occurred, a film could not be formed.

[Comparative Example 5] <Urethane resin composition>
After stirring and mixing 29.8 parts by mass of the alcohol solution (non-volatile content 30% by mass) of the alcohol-soluble urethane resin (A′-5) obtained in Comparative Synthesis Example 5 and 29.8 parts by mass of isopropyl alcohol, Urethane resin by gradually mixing 40.4 parts by mass of a mixture of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass occupied by SiO ₂ structure) in the mixture. A composition (5 ′) was obtained.

  However, since the obtained urethane resin composition (5 ') was poor in storage stability and agglomeration of the urethane resin, tetramethoxysilane and its partial hydrolysis condensate occurred, a film could not be formed.

[Comparative Example 6] <Urethane resin composition>
After stirring and mixing 13.8 parts by mass of an alcohol solution (non-volatile content 30% by mass) of the alcohol-soluble urethane resin (A′-5) obtained in Comparative Synthesis Example 5 and 13.8 parts by mass of isopropyl alcohol, Urethane resin by gradually mixing 72.4 parts by mass of 99% by mass of tetramethoxysilane and its partially hydrolyzed condensate and 1% by mass of methanol (51% by mass of SiO ₂ structure) in the mixture. A composition (6 ′) was obtained.

  However, since the obtained urethane resin composition (6 ') was poor in storage stability and agglomeration of the urethane resin, tetramethoxysilane and its partial hydrolysis condensate occurred, a film could not be formed.

(Method for evaluating film hardness)
The hardness of the films obtained in the examples and comparative examples was measured based on the scratch hardness (pencil method) of JIS K5600. A film having a hardness exceeding 7H was evaluated as a high hardness film.

(Evaluation method for adhesion of film to substrate)
The adhesion of the films obtained in Examples and Comparative Examples to the substrate was measured based on the JIS K5600 cross cut test method and evaluated according to the following evaluation criteria.

A: No peeling of the film was observed.
○: The area where the film was peeled off was less than 30% of the total grid area.
(Triangle | delta): The area from which the film peeled was 30 to less than 95% of the total grid area.
X: The area from which the film was peeled was 95% or more of the total grid area.

(Evaluation method of solvent resistance of film)
The same part of the surface of the film obtained in the above Examples and Comparative Examples was rubbed back and forth 50 times using a cotton swab soaked with methyl ethyl ketone (MEK) or ethanol (EtOH). The state of the film before rubbing and after rubbing was visually confirmed and evaluated according to the following evaluation criteria.

A: No change was observed in the state of the coating surface before and after rubbing.
○: Slight white turbidity was observed on the film surface before and after rubbing.
(Triangle | delta): The cloudiness of the film | membrane was recognized in about half the area of the film | membrane surface before and after rubbing. X: Before and after rubbing, almost the entire film became cloudy.
XX: Dissolving of the film was caused by rubbing 50 times.

(Evaluation method of scratch resistance of film)
Evaluation was performed using RUBING TESTER (produced by Taihei Rika Kogyo Co., Ltd.). Specifically, steel wool (made by Nippon Steel Wool Co., Ltd., trade name BONSTAR, product number No. 0000) was used as the wear body, and the wear surface was rubbed back and forth 20 times under the condition of a load of 500 g. The state of the film surface after rubbing was visually evaluated according to the following evaluation criteria.

A: The film was not damaged at all before and after 20 rounds of rubbing.
○: About 1 to 4 fine streak scratches were observed on the surface of the film before and after rubbing 20 times.
Δ: Five or more fine streak scratches were observed on the surface of the film before and after 20 rounds of rubbing.
X: Clear flaws were observed on the surface of the film before and after 20 rounds of rubbing, and the film caused a decrease in transparency of the film.
XX: After 20 rounds of rubbing, the film was torn and peeled off from the substrate.

  In addition, the coatings obtained in Examples 7 to 9 and Comparative Example 3 were rubbed 60 times in total by further rubbing 40 times after the 20 times of rubbing.

  The state of the film surface after the 60 times of rubbing was visually evaluated according to the following evaluation criteria.

A: The film was not scratched before and after rubbing 60 times.
○: About 1 to 4 fine streak scratches were observed on the film surface before and after the reciprocating rubbing 60 times.
Δ: Before and after the reciprocating 60 times of rubbing, 5 or more fine streaks were observed on the surface of the film.
X: A clear flaw was observed on the surface of the film before and after 60 rounds of rubbing, and the film caused a decrease in transparency of the film.
XX: After rubbing 60 times, the film was torn and peeled off from the substrate.

Footnotes in Tables 1 to 3 [Amount of inorganic component] of [Amount of organic component / amount of inorganic component] are the mass of silicon atom and the mass of oxygen atom contained in tetramethoxysilane and its partially hydrolyzed condensate, alcohol It is a total mass with the mass of the silicon atom and oxygen atom which comprise the hydrolyzable silyl group of a solution type urethane resin (A). The [organic component amount] is the total mass of silicon atoms and oxygen atoms constituting the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) from the mass of the alcohol-soluble urethane resin (A). Is the value obtained by subtracting.

Claims (18)

One or more types of hydrolysis selected from the group consisting of an alcohol-soluble urethane resin (A) having an oxyethylene structure and a hydrolyzable silyl group, a metal alkoxide (B-1) and a condensate thereof (B-2). A urethane resin composition containing a functional group-containing compound (B) and an alcohol (C), the silicon atom and oxygen atom constituting the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) And the total mass of the metal atom and oxygen atom of the hydrolyzable group-containing compound (B) is the total mass of the alcohol-soluble urethane resin (A) and the hydrolyzable group-containing compound (B). The urethane resin composition is characterized by being 50% by mass or more and 95% by mass or less. The said alcohol-soluble urethane resin (A) has 0.5-20 mass% hydrolyzable silyl group with respect to the total mass of the said alcohol-soluble urethane resin (A). The urethane resin composition described in 1. The urethane resin composition according to claim 1, wherein the alcohol-soluble urethane resin (A) has the hydrolyzable silyl group in a side chain of the alcohol-soluble urethane resin (A). The alcohol-soluble urethane resin (A) has a hydroxyl group or an isocyanate group at the molecular end by reacting the polyisocyanate (a1) with the polyol (a2) containing the oxyethylene structure-containing polyol (a2-1). Producing a urethane prepolymer (a3), then one or more selected from the group consisting of the urethane prepolymer (a3), an amino group-containing silane coupling agent and an isocyanate group-containing silane coupling agent, and as required The urethane resin composition according to claim 1, which is obtained by reacting with a chain extender. The said oxyethylene structure containing polyol (a2-1) is 1 or more types chosen from the group which consists of a polyether polyol which consists of a copolymer of ethylene oxide and tetrahydrofuran, and a polyoxyethylene polyol. The urethane resin composition as described. The urethane resin composition of Claim 4 whose mass ratio of the said oxyethylene structure containing polyol (a2-1) with respect to the total mass of the said polyol (a2) is 20-70 mass%. The urethane resin composition according to claim 1, wherein the alcohol-soluble urethane resin (A) has a number average molecular weight in the range of 5,000 to 300,000. The urethane resin composition according to claim 1, wherein the metal alkoxide (B-1) is a metal alkoxide having a structure represented by the following general formula (3), or a condensate thereof.
M (OR) n (3)
(M in the general formula (3) represents a metal atom, R represents an alkyl group, and n represents an integer in the range of 1 to the valence of the metal atom M.) The urethane resin composition according to claim 1, wherein the metal alkoxide (B-1) and / or a condensate thereof (B-2) is an alkoxysilyl group-containing compound and / or a condensate thereof. Total of the alcohol-soluble urethane resin (A) and the one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the metal alkoxide (B-1) and its condensate (B-2) The urethane resin composition of Claim 1 whose mass ratio of the said hydrolysable group containing compound (B) with respect to mass is 50-95 mass%. The urethane resin composition according to claim 1, wherein the alcohol (C) is an alcohol having an alkyl group having 1 to 7 carbon atoms. The coating agent which consists of a urethane resin composition of any one of Claims 1-11. The hard-coat agent which consists of a urethane resin composition of any one of Claims 1-11. Hardened | cured material obtained by hardening | curing the urethane resin composition of any one of Claims 1-11. Selected from the group consisting of a silanol group produced by hydrolysis of a hydrolyzable silyl group of the alcohol-soluble urethane resin (A), the metal alkoxide (B-1) and a condensate (B-2) thereof. The one or more hydrolyzable group-containing compounds (B) are bonded with a hydroxyl group produced by hydrolysis of an alkoxy group bonded to a metal atom to form a bond. Cured product. An alkoxy group bonded to a metal atom of one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the metal alkoxide (B-1) and its condensate (B-2) is an alkoxysilyl group. Furthermore, the hardened | cured material of Claim 14 whose hydroxyl group couple | bonded with the metal atom produced | generated by the said alkoxy group hydrolyzing is a silanol group. The urethane resin composition according to any one of claims 1 to 11 and, if necessary, a composition obtained by mixing water and an acid catalyst are applied to a substrate surface, The silanol group formed by hydrolyzing the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) and the metal alkoxide (B-1) by removing the alcohol (C) contained in And a hydroxyl group produced by hydrolysis of an alkoxy group bonded to a metal atom of one or more hydrolyzable group-containing compounds (B) selected from the group consisting of condensates thereof (B-2). The manufacturing method of the hardened | cured material characterized by forming a coupling | bonding. An alkoxy group bonded to a metal atom of one or more hydrolyzable group-containing compounds (B) selected from the group consisting of the metal alkoxide (B-1) and its condensate (B-2) is an alkoxysilyl group. The method for producing a cured product according to claim 17, wherein the hydroxyl group bonded to the metal atom produced by hydrolysis of the alkoxy group is a silanol group.