JP7066932B2 - Manufacturing method of composite resin, coating material, coating base material, insulating material, and composite resin - Google Patents

Description

The present invention relates to a composite resin, a coating material, a coating base material, an insulating material, and a method for producing the composite resin. The present invention relates to a coating base material having a coating layer containing a composite resin, an insulating material containing the composite resin, and a method for producing the composite resin.

Conventionally, a material containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group is known.

For example, Reference 1 describes the use of a composite resin containing a condensate of a fluoroalkyl group-containing oligomer having an alkoxysilyl group and a water-soluble cellulose ether as an oil-water separating material.

Japanese Unexamined Patent Publication No. 2017-160323

The present inventors have attempted to develop a new material containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group.

An object of the present invention is a composite resin having a unique affinity for polar substances and non-polar substances, a coating material containing the composite resin, a coating base material having a coating layer containing the composite resin, and the composite resin. It is an object of the present invention to provide an insulating material to be used and a method for producing the composite resin.

The composite resin according to the embodiment of the present invention contains a condensate obtained by condensing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and an amino resin.

In the formula, R ¹ and R ² independently represent-(CF ₂ ) p-Y group or -CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] q-OC ₃ F ₇ group, respectively, and Y Represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are each independently an integer of 0 to 10. R ³ , R ⁴ and R ⁵ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. m is an integer of 2 to 3.

The coating material according to the embodiment of the present invention contains the composite resin.

The coated base material according to the embodiment of the present invention has a base material and a coating layer containing the composite resin provided on the base material.

The insulating material according to the embodiment of the present invention contains the composite resin.

The method for producing a composite resin according to an embodiment of the present invention is the alkoxysilyl in a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and an amino resin. It comprises a step of carrying out a hydrolysis reaction of a group.

In the formula, R ¹ and R ² independently represent-(CF ₂ ) p-Y group or -CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] q-OC ₃ F ₇ group, respectively, and Y Represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are each independently an integer of 0 to 10. R ³ , R ⁴ and R ⁵ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. m is an integer of 2 to 3.

According to the present invention, a composite resin having a unique affinity for polar substances and non-polar substances, a coating material containing the composite resin, a coating base material having a coating layer containing the composite resin, and the composite resin are contained. It is possible to obtain an insulating material to be used and a method for producing the composite resin.

A mode for carrying out the present invention will be described.

The composite resin according to this embodiment is a condensation obtained by condensing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) (hereinafter, may be referred to as “fluoroalkyl group-containing oligomer”). Includes things and amino resins.

In the formula, R ¹ and R ² independently represent-(CF ₂ ) p-Y group or -CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] q-OC ₃ F ₇ group, respectively, and Y Represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are each independently an integer of 0 to 10. R ³ , R ⁴ and R ⁵ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. m is an integer of 2 to 3.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R ³ , R ⁴ and R ⁵ in the general formula (1) are methyl group, ethyl group, propyl group, butyl group and pentyl. Including groups and the like.

In the-(CF ₂ ) p-Y group or -CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] q-OC ₃ F ₇ group represented by R ¹ and R ² in the general formula (1). It is preferable that p and q are integers of 0 to 3. In particular, it is preferable that R ¹ and R ² are -CF (CF ₃ ) -OC ₃ F ₇ units.

The fluoroalkyl group-containing oligomer represented by the general formula (1) can be produced, for example, by reacting trialkoxyvinylsilane such as trimethoxyvinylsilane with fluoroalkanoyl peroxide (for example, JP-A-2002-338691). See Japanese Patent Application Laid-Open No. 2010-77383).

Since the composite resin contains a condensate of a fluoroalkyl group-containing oligomer and an amino resin, it has a unique affinity for polar substances and non-polar substances. For example, the composite resin has good adhesion to various substrates such as a metal substrate, a glass substrate, and a resin substrate. Although the condensate of the fluoroalkyl group-containing oligomer alone does not exhibit such good adhesion to various substrates, various fluoroalkyl group-containing oligomers are composited with the amino resin in the composite resin. Good adhesion to the substrate is exhibited. The mechanism of how the fluoroalkyl group-containing oligomer and the amino resin are composited in the composite resin has not been elucidated. However, it is speculated that the amino groups derived from the amino resin are dispersed in the composite resin, which contributes to the specific affinity for polar substances and non-polar substances such as good adhesion to various substrates. Will be done.

The amino resin contained in the composite resin is not particularly limited as long as it is a resin having an amino group. The amino resin contained in the composite resin preferably contains at least one selected from the group consisting of melamine resin, aniline resin, benzoguanamine resin, and urea resin. It is particularly preferable that the amino resin contains a melamine resin.

The melamine resin is a condensate of melamine and formaldehyde, or a thermosetting resin obtained by polymerizing the condensate. Specific examples of the melamine resin include methylated butylated melamine formaldehyde resin, methylated melamine formaldehyde resin, butylated melamine formaldehyde resin and the like. Specific products of melamine resin include, for example, product names Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, and My. Coat 715, Cymel 701, Cymel 267, Cymel 285, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 211, Cymel 254, Cymel 204, My Coat 212, Cymel 202, Cymel 207, My Coat 506, and My Coat. 508; Product names manufactured by DIC Corporation AMIDIR J-820-60, AMIDIR L-109-65, AMIDIR L-117-60, AMIDIR L-127-60, AMIDIR 13-548, AMIDIR G-821-60, AMIDIR L -110-60, AMIDIR L-125-60, AMIDIR L-166-60B, AMIDIR L-105-60, AMIDIR S-695, and AMIDIR S-683-IM; and product name MW-manufactured by Sanwa Chemical Co., Ltd. 30MLF, MW-30M, MW-30LF, MW-30, MW-22, MS-11, MW-12LF, MS-001, MZ-351, MX-730, MX-750, MX-706, and MX-035. And so on.

The aniline resin is a condensate of aniline and formaldehyde, or a thermosetting resin obtained by polymerizing the condensate. Specific examples of the aniline resin include methylated aniline formaldehyde resin, butylated aniline formaldehyde resin, methylated butylated aniline formaldehyde resin and the like.

The benzoguanamine resin is a condensate of benzoguanamine and formaldehyde, or a thermosetting resin obtained by polymerizing this condensate. Specific examples of the benzoguanamine resin include methylated benzoguanamine formaldehyde resin, butylated benzoguanamine formaldehyde resin, methylated butylated benzoguanamine formaldehyde resin, methylated ethylened benzoguanamine formaldehyde resin and the like. Specific products of the benzoguanamine resin include, for example, the product names Cymel 1123, My Coat 102, My Coat 105, My Coat 106, and My Coat 1128 manufactured by Nippon Cytec Industries Co., Ltd .; the product name AMIDIR TD-126 manufactured by DIC Corporation. And AMIDIR 15-594; and product names BL-60, BX-4000, etc. manufactured by Sanwa Chemical Co., Ltd.

The urea resin is a condensate of urea and formaldehyde, or a thermosetting resin obtained by polymerizing the condensate. Specific examples of the urea resin include methylated urea formaldehyde resin, butylated urea formaldehyde resin, methylated butylated urea formaldehyde resin and the like. Specific products of urea resin include, for example, UFR65 and UFR300 manufactured by Cytec Industries, Ltd., and AMIDIR P-138, AMIDIR P-196-M, and AMIDIR G-1850 manufactured by DIC Corporation. Can be mentioned.

The content of the amino resin contained in the composite resin is preferably 0.1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the condensate of the fluoroalkyl group-containing oligomer, and is preferably 1 part by mass or more and 500 parts by mass. More preferably, it is less than or equal to a part. When the content of the amino resin is 1 part by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the condensate of the fluoroalkyl group-containing oligomer, the composite resin has a unique affinity for polar substances and non-polar substances. Can have.

The composite resin is preferably in the form of particles. In this case, the average particle size of the composite resin is preferably 2000 nm or less. When the average particle size of the composite resin is 2000 nm or less, the composite resin can have high transparency. The average particle size of the composite resin is more preferably 1000 nm or less. The average particle size of the composite resin is preferably 0.01 nm or more. When the average particle size of the composite resin is 0.01 nm or more, the composite resin can have good dispersibility in various dispersion solvents when the composite resin is used as a coating material or an insulating material. The average particle size of the composite resin is more preferably 0.05 nm or more, and particularly preferably 0.6 nm or more. The average particle size of the composite resin is a volume-based median size calculated from the measured value of the particle size distribution by the laser diffraction / scattering method, and can be obtained by using a commercially available laser analysis / scattering type particle size distribution measuring device.

The composite resin according to the present embodiment is subjected to a hydrolysis reaction of an alkoxysilyl group in a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the general formula (1) and an amino resin. It is preferable to obtain it in. That is, in the method for producing a composite resin of the present embodiment, the alkoxysilyl group is hydrolyzed in a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxyryl group represented by the general formula (1) and an amino resin. Includes a step of performing a decomposition reaction.

In the composite resin, the alkoxysilyl group of the fluoroalkyl group-containing oligomer is hydrolyzed in the reaction raw material solution containing the fluoroalkyl group-containing oligomer and the amino resin, so that the fluoroalkyl group-containing oligomer and the amino resin are composited. Obtained by doing. Since the mechanism of compositing and the structure of the composited fluoroalkyl group-containing oligomer and the amino resin have not been elucidated, the structure or characteristics of the composite resin cannot be literally specified. However, as described above, it is presumed that the amino groups derived from the amino resin are dispersed in the composite resin. It is considered that the dispersion of the amino groups in this way causes the amino groups to participate in hydrogen bonds, thereby exhibiting adhesion to various substrates.

The amino resin in the reaction raw material solution may be an amino resin similar to the amino resin contained in the composite resin.

The amino resin in the reaction raw material solution is preferably liquid at 25 ° C. or dissolved in the reaction raw material solution at 25 ° C. That is, it is preferable that the amino resin used as a raw material has a property of being liquid at 25 ° C. or a property of being soluble in a reaction raw material solution at 25 ° C. In this case, the fluoroalkyl group-containing oligomer and the amino resin can be better composited.

The amino resin in the reaction raw material solution preferably contains at least one selected from the group consisting of melamine resin, aniline resin, benzoguanamine resin, and urea resin. Specific examples of the melamine resin include methylated butylated melamine formaldehyde resin, methylated melamine formaldehyde resin, butylated melamine formaldehyde resin and the like. Specific examples of the aniline resin include methylated aniline formaldehyde resin, butylated aniline formaldehyde resin, methylated butylated aniline formaldehyde resin and the like. Specific examples of the benzoguanamine resin include methylated benzoguanamine formaldehyde resin, butylated benzoguanamine formaldehyde resin, methylated butylated benzoguanamine formaldehyde resin, methylated ethylened benzoguanamine formaldehyde resin and the like. Specific examples of the urea resin include methylated urea formaldehyde resin, butylated urea formaldehyde resin, methylated butylated urea formaldehyde resin and the like. It is particularly preferable that the amino resin contains a melamine resin.

The content of the amino resin in the reaction raw material solution is preferably 0.1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the fluoroalkyl group-containing oligomer represented by the general formula (1). In this case, the composite resin may have a unique affinity for polar and non-polar substances. The content of the amino resin is more preferably 1 part by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the fluoroalkyl group-containing oligomer, and particularly preferably 2 parts by mass or more and 200 parts by mass or less.

In the preparation of the reaction raw material solution, the order of adding the fluoroalkyl group-containing oligomer and the amino resin is not particularly limited.

The reaction temperature when carrying out the hydrolysis reaction is preferably −5 ° C. or higher and 50 ° C. or lower. By carrying out the hydrolysis reaction at −5 ° C. or higher, it is possible to prevent the hydrolysis rate from becoming too slow and increase the reaction efficiency. Further, by carrying out the hydrolysis reaction at 50 ° C. or lower, the stability of the composite resin can be improved. The reaction time for carrying out the hydrolysis reaction is not particularly limited and can be appropriately selected. The reaction time is preferably in the range of, for example, 1 to 72 hours, and more preferably in the range of 1 to 50 hours.

The hydrolysis reaction is preferably carried out using a reaction solvent. That is, the reaction raw material solution preferably contains a reaction solvent. In this case, the hydrolysis reaction can be carried out efficiently. Examples of reaction solvents include lower alcohols such as water, methanol, ethanol and isopropyl alcohol. These solvents may be used alone or in combination of two or more as a mixed solvent. In particular, it is preferable to use a mixed solvent of water and methanol. The reaction solvent may be removed by reducing the pressure of the reaction solution containing the composite resin obtained after performing the hydrolysis reaction in the reaction raw material solution by a conventional method. Further, after the completion of the hydrolysis reaction, the reaction solution containing the composite resin may be used as it is as a coating material described later without removing the reaction solvent.

The method of the hydrolysis reaction is not particularly limited, and may be carried out under a catalyst such as an acid catalyst and a base catalyst, or may be carried out under a non-catalyst. The obtained composite resin exhibits different properties depending on the presence or absence of a catalyst in the hydrolysis reaction and the type of catalyst. Therefore, the method of hydrolysis reaction may be appropriately selected according to the intended use.

When the hydrolysis reaction is carried out without a catalyst, the composite resin obtained by the hydrolysis reaction under the non-catalyst has higher hydrophilicity and oil repellency than the composite resin obtained by the hydrolysis reaction under the base catalyst. It can be done. The composite resin obtained by the hydrolysis reaction under a catalyst may have hydrophilicity such that the contact angle of the composite resin with water measured by the method described later is 90 ° or less. Further, the composite resin may have oil repellency such that the contact angle of the composite resin with respect to dodecane measured by the method described later is 21 ° or more. Since the composite resin obtained by the hydrolysis reaction under no catalyst can have hydrophilicity and oil repellency, when a coating material containing this composite resin is used to form a coating layer, it is difficult to fog and fingerprints and the like are formed. It is possible to obtain a coating layer to which dirt containing an oily component does not easily adhere.

In addition, the composite resin obtained by the hydrolysis reaction under no catalyst has good transparency. Therefore, by using a coating material containing this composite resin, a highly transparent coating layer can be formed.

Further, the composite resin obtained by the hydrolysis reaction under no catalyst is a resin base material containing a metal base material, a glass base material, a PP (polypropylene) resin, an ABS (acrylonitrile / butadiene / styrene copolymer) resin, and the like. Has good adhesion to various substrates. Therefore, by using a coating material containing this composite resin, it is possible to form a coating layer having high adhesion to various substrates.

When the hydrolysis reaction is carried out under an acid catalyst, the acid catalyst is not particularly limited as long as it can hydrolyze the alkoxysilyl group in the fluoroalkyl group-containing oligomer. Examples of acid catalysts include sulfuric acid, hydrochloric acid, nitric acid, acetic acid and the like.

The composite resin obtained by the hydrolysis reaction under an acid catalyst has the same characteristics as the composite resin obtained by the hydrolysis reaction under a non-catalyst. That is, the composite resin obtained by the hydrolysis reaction under an acid catalyst may have hydrophilicity and oil repellency. Further, this composite resin has good transparency and can be applied to various base materials such as a metal base material, a glass base material, a resin base material containing PP (polypropylene) resin, ABS (acrylonitrile, butadiene, styrene copolymer) resin and the like. Has good adhesion.

When the hydrolysis reaction is carried out under a base catalyst, the base catalyst is not particularly limited as long as it can hydrolyze the alkoxysilyl group in the fluoroalkyl group-containing oligomer. Examples of the base catalyst include aqueous ammonia, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate and the like.

The composite resin obtained by the hydrolysis reaction under a base catalyst may have high water repellency and oil-friendly property as compared with the composite resin obtained by the hydrolysis reaction under a non-catalyst and an acid catalyst. The composite resin obtained by the hydrolysis reaction under a base catalyst may have water repellency such that the contact angle of the composite resin with water measured by the method described later is 91 ° or more. Further, the composite resin obtained by the hydrolysis reaction under a base catalyst may have lipophilicity such that the contact angle of the composite resin with respect to dodecane measured by the method described later is 20 ° or less. Since the composite resin obtained by the hydrolysis reaction under a base catalyst can have water repellency and lipophilicity, for example, this composite resin can be used as an oil-water separator. Further, the composite resin obtained by the hydrolysis reaction under a base catalyst may have superhydrophobicity and superlipophilicity. The fact that the composite resin has superhydrophobicity means that the contact angle of the composite resin with water measured by the method described later is 150 ° or more. Further, the fact that the composite resin has super lipophilicity means that the contact angle of the composite resin with respect to dodecane measured by the method described later is 5 ° or less. The composite resin having superhydrophobicity and superlipophilicity can be particularly preferably used in the application of an oil-water separating material.

A coating material according to an embodiment of the present invention will be described.

The coating material of this embodiment contains a composite resin. As described above, remove the reaction solvent from the reaction solution containing the composite resin after the hydrolysis reaction of the alkoxysilyl group in the reaction raw material solution containing the fluoroalkyl group-containing oligomer, the amino resin and the reaction solvent. It may be used as it is as a coating material without using it. Further, the reaction solvent may be removed from the reaction solution containing the composite resin by a conventional method to obtain the composite resin, and then the dispersion liquid in which the composite resin is dispersed in the dispersion medium may be used as the coating material.

The coating material may contain a component other than the composite resin depending on the intended use. The coating material may contain, for example, an additive such as a silane coupling agent. Additives can be appropriately selected depending on the use of the coating material. For example, by adding an antibacterial silane coupling agent to the coating material, antibacterial properties can be imparted to the coating layer formed from the coating material.

As described above, the obtained composite resin exhibits different characteristics depending on the presence or absence of a catalyst in the hydrolysis reaction and the type of catalyst. Therefore, the characteristics of the composite resin can be selected according to the application when used as a coating material. Therefore, the coating material containing the composite resin is an optical member such as an antireflection film, an optical filter, an optical lens, a liquid crystal display, a CRT display, a projection television, a plasma display, and an EL display used for parts of optical products, and wallpaper. , And can be used for signs and the like.

A coated substrate according to an embodiment of the present invention will be described.

The coating base material of the present embodiment has a base material and a coating layer containing a composite resin provided on the base material.

The base material is not particularly limited as long as it has good adhesion to the coating layer containing the composite resin. Examples of raw materials for base materials are metals; inorganic substances such as glass fiber, silica, silica gel, alumina, slag wool, molecular sieve, zeolite, activated charcoal, diatomaceous soil, sand, and asbestos; natural polymers such as cellulose, wool, cotton, and silk. Condensed or additive polymerized polymers such as polyurethane, polyethylene terephthalate, nylon and polycarbonate; include ethylenically unsaturated polymer polymers such as polyethylene, polypropylene, vinyl chloride and vinyl acetate.

The shape of the base material is not particularly limited, and may be, for example, a strip-like shape, a sponge-like shape, a ribbon-like shape, a fibril-like shape, a web-like shape, a mat-like shape, a cotton cloth-like shape, a non-woven fabric-like shape, or the like.

A coated base material can be obtained by forming a coating layer containing a composite resin on such a base material. The coating layer can be formed by using the coating material containing the above-mentioned composite resin. For example, a coating layer can be formed by applying a coating material to a substrate and drying it.

The coated substrate can be used for various purposes depending on the characteristics of the coating layer. For example, a coated base material provided with a coating layer containing a composite resin having high water repellency and lipophilicity can be used as an oil-water separating material for separating a mixed liquid of water and an oil-based component. When the coated base material is used as the oil-water separating material, for example, the column can be filled with the coating base material as the oil-water separating material, and the mixed liquid can be charged into the column to separate water and the oil-based component.

The insulating material according to the embodiment of the present invention will be described.

The insulating material of this embodiment contains a composite resin. Since the composite resin can have high adhesion to metal, the insulating material containing the composite resin can be suitably used for applications such as solder resist and inner layer insulating material.

The insulating material may be, for example, a resin composition containing a composite resin. The resin composition can contain at least one of a thermosetting resin and a photocurable resin in addition to the composite resin. The resin composition includes, for example, a carboxyl group-containing resin, an unsaturated compound having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator, an epoxy compound, an organic filler, and a coupling agent, in addition to the composite resin. , And components such as solvents can be contained. The resin composition further includes an inorganic filler, a curing agent, an adhesion imparting agent, a curing accelerator, a coloring agent, a leveling agent, a thixotropic agent, a polymerization inhibitor, an antihalation agent, a flame retardant, an antifoaming agent, an antioxidant, and a surfactant. Ingredients such as an activator and a polymer dispersant may be contained as needed.

For example, a film is formed from a resin composition containing a composite resin on a conductor wiring of a printed wiring board provided with an insulating layer and a conductor wiring, and this film is cured by at least one method of thermal curing and photocuring. It can be allowed to form a cured film. For example, a solder resist layer can be formed by subjecting a film formed from a resin composition to an exposure and development treatment and then a thermosetting treatment.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

(1) Fluoroalkyl group-containing oligomer As the fluoroalkyl group-containing oligomer (hereinafter, may be referred to as “VM”), the one shown in Table 1 below was used.

In Table 1, the molecular weight is the average molecular weight by gel permeation chromatography (GPC, polystyrene conversion).

(2) Synthesis of composite resin (2-1) Synthesis examples 1-9
VM, methylated butylated melamine formaldehyde resin (manufactured by Nippon Cytec Industries Co., Ltd., product name Cymel 235, number average molecular weight 630, degree of polymerization 1.4, liquid at 25 ° C), and methanol in the amounts shown in Table 2 below. It was charged in a container and a reaction raw material solution was prepared. Then, the reaction raw material solution was stirred at 25 ° C. for 5 minutes using a magnetic stirrer. Then, in the reaction raw material solutions of Synthesis Examples 1 to 3, stirring was further performed at 25 ° C. for 12 hours using a magnetic stirrer, and this was used as a reaction solution sample. In the reaction raw material solutions of Synthesis Examples 4 to 6, the amount shown in Table 2 below was 25 wt% aq. NH ₃ was added and the reaction raw material solution was stirred at 25 ° C. for 12 hours using a magnetic stirrer. The reaction solution thus obtained was used as a reaction solution sample of Synthesis Examples 4 to 6. In the reaction raw material solutions of Synthesis Examples 7 to 9, 1 mol / L HCl was added in the amount shown in Table 2 below, and the reaction raw material solution was stirred at 25 ° C. for 12 hours using a magnetic stirrer. The reaction solution thus obtained was used as a reaction solution sample of Synthesis Examples 7 to 9.

The average particle size of the composite resin contained in the reaction solution samples of Synthesis Examples 1 to 9 was measured using a laser analysis / scattering type particle size distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., product number ELSZ-2000ZS). Since the average particle size of the composite resin contained in the reaction solution samples of Synthesis Examples 1, 2, 4, 5, 7 and 8 was less than the detection limit of 0.6 nm, it could not be measured. The average particle size of the composite resin contained in the reaction solution samples of Synthesis Examples 3, 6 and 9 is as shown in Table 2 below.

(2-2) Synthesis Example 10
VM and methanol were charged in a container in the amounts shown in Table 2 below to prepare a reaction raw material solution. Then, the reaction raw material solution was stirred at 25 ° C. for 5 minutes using a magnetic stirrer. Then, the mixture was further stirred at 25 ° C. for 12 hours using a magnetic stirrer, and this was used as a reaction solution sample.

(3) Preparation of test piece (3-1) Examples 1 to 9 and Comparative Example 1
The test pieces of Examples 1 to 9 and Comparative Example 1 were prepared as follows. A glass substrate, a PP (polypropylene) substrate, and an ABS (acrylonitrile-butadiene-styrene copolymer) substrate were immersed in each of the reaction solution samples of Synthesis Examples 1 to 10 at 25 ° C. for 1 minute. After each substrate was pulled up from the reaction solution sample, it was naturally dried, and further vacuum dried at 20 ° C. overnight, and Examples 1 to 9 and Comparative Example 1 in which a layer formed from the reaction solution was provided on the substrate. I got a test piece of.

(3-2) Examples 10 to 18 and Comparative Example 2
The test pieces of Examples 10 to 18 and Comparative Example 2 were prepared as follows. A glass substrate, a PP (polypropylene) substrate, and an ABS (acrylonitrile-butadiene-styrene copolymer) substrate were immersed in each of the reaction solution samples of Synthesis Examples 1 to 10 at 25 ° C. for 1 minute. After pulling up each substrate from the reaction solution sample, it was naturally dried, and further vacuum dried at 20 ° C. overnight. Then, the glass substrate was heat-treated at 150 ° C. for 1 hour, the PP substrate was heat-treated at 80 ° C. for 1 hour, and the ABS substrate was heat-treated at 60 ° C. for 1 hour. As a result, the test pieces of Examples 10 to 18 and Comparative Example 2 in which the layer formed from the reaction solution was provided on the substrate were obtained.

(3-3) Example 19 and Comparative Example 3
(3-3-1) Synthesis of carboxyl group-containing resin A bisphenol fluorene-type epoxy compound (represented by the following formula (2)) is placed in a four-necked flask equipped with a reflux cooler, a thermometer, an air blow tube and a stirrer. Epoxy compounds having an epoxy equivalent of 250 g / eq, in which R ₁ to R ₈ in the formula (2) are all hydrogen) 250 parts by mass, acrylic acid 72 parts by mass, triphenylphosphine 1.5 parts by mass, methylhydroquinone 0. 2 parts by mass, 60 parts by mass of propylene glycol monomethyl ether acetate, and 140 parts by mass of diethylene glycol monoethyl ether acetate were added. A mixture was prepared by stirring these under air bubbling. The mixture was heated at 115 ° C. for 12 hours with stirring in the flask under air bubbling. This prepared a solution of the intermediate. Subsequently, 60.8 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride, 58.8 parts by mass of 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride was added to the solution of the intermediate in the flask. 38.7 parts by mass and 38.7 parts by mass of propylene glycol monomethyl ether acetate were added. These were heated at 115 ° C. for 6 hours while stirring under air bubbling, and further heated at 80 ° C. for 1 hour while stirring under air bubbling. As a result, a 65% by mass solution of the carboxyl group-containing resin was obtained. The degree of polydispersity (Mw / Mn) of the carboxyl group-containing resin was 2.15, the weight average molecular weight (Mw) was 3096, and the acid value was 105 mgKOH / g.

(3-3-2) Preparation of Photosensitive Resin Composition The components shown in the “Composition” column of Table 5 below are used in Example 19 and Comparative Example 3 by stirring and mixing in a flask at 35 ° C. A photosensitive resin composition was obtained.

The details of the components shown in "Composition" in Table 5 are as follows.
-Unsaturated compound: trimethylolpropane triacrylate.
-Photopolymerization initiator A: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO.
-Photopolymerization initiator B: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product number Irgacure 184.
-Photopolymerization initiator C: 4,4'-bis (diethylamino) benzophenone.
Epoxy resin A: Biphenyl-type crystalline epoxy resin, manufactured by Mitsubishi Chemical Corporation, product number YX-4000, melting point 105 ° C., epoxy equivalent 187 g / eq.
Epoxy resin B: Bisphenol type crystalline epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YSLV-80XY, melting point 75-85 ° C., epoxy equivalent 192 g / eq.
-Epoxy resin C solution: A long-chain carbon chain-containing bisphenol A type epoxy resin (manufactured by DIC Co., Ltd., product number EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq) is converted into diethylene glycol monoethyl ether acetate with a solid content of 90%. Dissolved solution (epoxy equivalent in terms of solid content 90% is 455.56 g / eq).
-Dispersion liquid of organic filler: A dispersion liquid (manufactured by JSR Corporation, product number) in which crosslinked rubber (NBR) having an average primary particle diameter of 0.07 μm is dispersed in methyl ethyl ketone at a content of 15% by weight based on the total amount of the dispersion liquid. XER-91-MEK, acid value 10.0 mgKOH / g).
-Silane coupling agent: 3-glycidoxypropyltrimethoxysilane.
-Antioxidant: Hindered phenolic antioxidant, manufactured by BASF, product number IRGANOX 1010.
-Surfactant: DIC Corporation, product number Megafuck F-477.
-VM / amino composite solution: Reaction solution of Synthesis Example 2.
-Solvent: Diethylene glycol monoethyl ether acetate.

(3-3-3) Preparation of Test Piece Using the photosensitive resin compositions of Example 19 and Comparative Example 3, a test piece was prepared as follows.

The photosensitive resin composition was applied to a film made of polyethylene terephthalate with an applicator and then dried by heating at 95 ° C. for 25 minutes to form a dry film having a thickness of 30 μm on the film.

A glass epoxy copper-clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 μm was prepared. A comb-shaped electrode having a line width / space width of 30 μm / 30 μm was formed as a conductor wiring on this glass epoxy copper-clad laminate by a subtractive method, thereby obtaining a core material. The conductor wiring was roughened by dissolving and removing the surface layer portion of the conductor wiring of the core material having a thickness of about 1 μm with an etching agent (organic acid-based micro-etching agent manufactured by MEC Co., Ltd., product number CZ-8101). A dry film was heat-laminated on the entire surface of this core material with a vacuum laminator. The conditions for heat laminating are 0.5 MPa, 80 ° C., and 1 minute. As a result, a film having a film thickness of 30 μm made of a dry film was formed on the core material. A negative mask having a non-exposed portion of a pattern including a circular shape with a diameter of 60 μm is directly applied to this film from a polyethylene terephthalate film, and ultraviolet rays are applied to the film via the negative mask under the condition of 250 mJ / cm ² . Was irradiated. After the exposure, the polyethylene terephthalate film was peeled off from the dry film (film). Next, the film after exposure was subjected to a developing treatment. In the development treatment, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed onto the film at an injection pressure of 0.2 MPa for 90 seconds. Subsequently, the film was washed by injecting pure water at an injection pressure of 0.2 MPa for 90 seconds. As a result, the unexposed portion of the film was removed. Subsequently, the film was heated at 180 ° C. for 120 minutes. As a result, a layer made of a cured product of the photosensitive resin composition (which can be said to be a cured product of the dry film) was formed on the core material. This gave a test piece.

(4) Evaluation test (4-1) Transparency For each of the test pieces of Examples 1 to 18 and Comparative Examples 1 and 2, the original substrate (glass substrate, PP) on which the layer formed from the reaction solution was not provided was provided. Compared with the substrate and ABS substrate), the transparency is visually evaluated according to the following evaluation criteria, and is shown in the “Transparency” column of Tables 3 and 4 below.
A: It has the same transparency as the original substrate.
B: Has lower transparency than the original substrate.

(4-2) Adhesiveness In accordance with JIS K 5600-5-6, make a notch of 25 squares in each of the test pieces of Examples 1 to 18 and Comparative Examples 1 and 2, and attach an adhesive tape on them. After that, the adhesive tape was peeled off within 5 minutes. The peeling of the layer formed from the reaction solution was visually confirmed. The results are evaluated as follows and are shown in the "Adhesion" column of Tables 3 and 4 below.
A: In 22 or more of the 25 cells, the layer formed from the reaction solution remained without peeling.
B: In 10 or more and less than 22 cells out of 25 cells, the layer formed from the reaction solution remained without peeling.
C: In less than 10 cells out of 25 cells, the layer formed from the reaction solution remained without peeling.

(4-3) Contact angle (Dodecane)
Dodecane was brought into contact with each of the test pieces of Examples 1 to 18 and Comparative Examples 1 and 2, and the contact angle after 30 minutes was measured using a contact angle meter (Drop Master.300, manufactured by Kyowa Interface Science Co., Ltd.). It was measured. The results are shown in the "Dodecane" column of Tables 3 and 4 below. The contact angles of the original glass substrate, PP substrate, and ABS substrate without the layer formed from the reaction solution with respect to dodecane were 0 °, 0 °, and 9 °, respectively.

N / A in the "contact angle (dodecane)" column of Tables 3 and 4 means that the contact angle with respect to dodecane was not measured.

(4-4) Contact angle (water)
Water was brought into contact with each of the test pieces of Examples 1 to 18 and Comparative Examples 1 and 2, and the contact angle after 30 minutes was measured using a contact angle meter (Drop Master.300, manufactured by Kyowa Interface Science Co., Ltd.). It was measured. The results are shown in the "Dodecane" column of Tables 3 and 4 below. The contact angles of the original glass substrate, PP substrate, and ABS substrate without the layer formed from the reaction solution with respect to water were 29 °, 38 °, and 80 °, respectively.

N / A in the "contact angle (water)" column of Tables 3 and 4 means that the contact angle with respect to water was not measured.

(4-5) Plating resistance After forming a nickel plating layer on the externally exposed portion of the conductor wiring of the test pieces of Example 19 and Comparative Example 3 using a commercially available electroless nickel plating bath, A gold-plated layer was formed using a commercially available electroless gold-plated bath. As a result, a metal layer composed of a nickel-plated layer and a gold-plated layer was formed. The layer made of the cured product and the metal layer were visually observed. In addition, a cellophane adhesive tape peeling test was performed on the layer made of the cured product. The results are evaluated as follows and are shown in the "Plating resistance" column of Table 5 below.
A: No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and the layer made of the cured product was not peeled off by the cellophane adhesive tape peeling test.
B: Discoloration was observed in the layer made of the cured product, but the layer made of the cured product was not peeled off by the cellophane adhesive tape peeling test.
C: Lifting of the layer made of the cured product was observed, and the layer made of the cured product was peeled off by the cellophane adhesive tape peeling test.

(4-6) Line Insulation While applying a bias voltage of DC30V to the conductor wiring (comb-shaped electrode) in the test pieces of Example 19 and Comparative Example 3, the test piece was heated at 121 ° C. and 97% R. H. Was exposed to the test environment for 120 hours. The electrical resistance values between the comb-shaped electrodes of the cured product layer under this test environment are constantly measured, and the results are evaluated according to the following evaluation criteria, and are shown in the "Line insulation" column of Table 5 below. ..
A: From the start of the test to the elapse of 100 hours, the electrical resistance value was always maintained at ¹⁰⁶ Ω or higher.
B: The electric resistance value was always maintained at ¹⁰⁶ Ω or more from the start of the test until 80 hours passed, but the electric resistance value became less than ¹⁰⁶ Ω before 100 hours passed from the start of the test.
D: The electrical resistance value became less than ¹⁰⁶ Ω before 80 hours had passed from the start of the test.

(4-7) PCT (Pressure Cooker Test)
The test pieces of Example 19 and Comparative Example 3 were heated at 121 ° C. and 100% R. H. After being left in the above environment for 100 hours, the appearance of the layer made of the cured product is evaluated according to the following evaluation criteria, and the results are shown in the “PCT” column of Table 5 below.
A: No abnormality was found in the layer made of the cured product.
B: Discoloration was observed in the layer made of the cured product.
C: A large discoloration was observed in the layer made of the cured product, and some swelling occurred.

(4-8) Roughing resistance With respect to the test pieces of Example 19 and Comparative Example 3, the outer surface of the layer made of a cured product is roughened by the following procedure based on the desmear treatment that is common in the pre-plating process. rice field. The swelling treatment is performed at 60 ° C. for 5 minutes using a swelling treatment liquid (Atotech Japan Co., Ltd., Swering Dip Security Guns P) commercially available as a swelling liquid for desmia, and the surface of the layer made of the cured product is swelled. I let you. Then, the swollen surface was washed with hot water. Subsequently, a roughening treatment was performed at 80 ° C. for 10 minutes using an oxidizing agent (Atotech Japan Co., Ltd., Concentrate Compact CP) containing potassium permanganate, which is commercially available as a desmia solution, and after washing with hot water. The surface of the layer made of the cured product of No. 1 was roughened. The surface of the layer made of the roughened cured product is washed with hot water, and a neutralizing solution (Reduction Solution Security P manufactured by Atotech Japan Co., Ltd.) is used on the surface of the layer made of the cured product. The residue of the desmear solution was removed by performing a neutralization treatment at 40 ° C. for 5 minutes. Then, the surface of the layer made of the cured product after neutralization was washed with water, and the thickness of the layer made of the cured product of the photosensitive resin composition having a roughened surface was measured. The results are evaluated as the roughening resistance to the Desmia liquid according to the following evaluation criteria, and are shown in the "Roughing resistance" column of Table 5 below.
A: The decrease in the thickness of the layer made of the cured product due to roughening is less than 3 μm.
B: The decrease in the thickness of the layer made of the cured product due to roughening is 3 μm or more and less than 6 μm.
C: The decrease in the thickness of the layer made of the cured product due to roughening is 6 μm or more.

(4-9) Adhesion to Copper Plated Layer The test pieces of Example 19 and Comparative Example 3 were roughened in the same manner as in (4-8) above. rice field. Then, using a commercially available chemical solution, initial wiring was formed on the surface of the layer made of the roughened cured product by electroless copper plating. The test piece provided with this initial wiring was heated at 150 ° C. for 1 hour. Next, by electrolytic copper plating treatment, copper having a thickness of 33 μm was directly deposited on the initial wiring from a commercially available chemical solution at a current density of 2 A / dm ² , and then a test piece on which copper was deposited was deposited at 180 ° C. for 30 minutes. It was heated to form a copper-plated layer. The adhesion between the formed copper-plated layer and the layer made of the cured product is evaluated according to the following evaluation criteria, and the results are shown in the "Adhesion to the copper-plated layer" column of Table 5 below. If blister is not confirmed on the test piece during both heating after electroless copper plating and electrolytic copper plating, the adhesion strength between the copper plating layer and the cured product is determined in accordance with JIS C6481. It was measured.
A: No blister was confirmed during heating after the electroless copper plating treatment and during heating after the electrolytic copper plating treatment, and the adhesion strength was 0.6 kN / m or more.
B: No blister was confirmed during heating after the electroless copper plating treatment and during heating after the electrolytic copper plating treatment, and the adhesion strength was less than 0.6 kN / m.
C: Blister was confirmed either during heating after electroless copper plating treatment or during heating after electrolytic copper plating treatment.

As the results of the transparency evaluation test shown in Tables 3 and 4, the composite resin composited under the non-catalyst and the acid catalyst has good transparency. On the other hand, the transparency of the composite resin composited under the base catalyst is lower than that of the composite resin composited under the non-catalyst and the acid catalyst. Therefore, the composite resin composited under a non-catalyst and an acid catalyst can be suitably used for applications requiring high transparency.

The composite resins of Examples 1 to 18 have excellent adhesion to glass substrates, PP substrates, and ABS substrates as compared to the non-composited fluoroalkyl group-containing oligomers of Comparative Examples 1 and 2. Furthermore, the composite resin composited under the non-catalyst and the acid catalyst has better adhesion to the glass substrate, PP substrate, and ABS substrate as compared with the composite resin composited under the base catalyst. ..

Composite resins composited under non-catalyst and acid catalyst tend to have oil repellency. Further, the composite resin composited under a non-catalyst and an acid catalyst has higher hydrophilicity than the composite resin composited under a base catalyst. On the other hand, the composite resin composited under a base catalyst has lower oil repellency than the composite resin composited under a non-catalyst and an acid catalyst. Further, the composite resin composited under the base catalyst tends to have high water repellency. In particular, Examples 5 and 14 in which a layer formed from a reaction solution containing a composite resin is provided on a glass substrate have superhydrophobicity and superlipophilicity, so that such a coating substrate is oil-water separated. It can be used particularly preferably for the application.

Claims (13)

It contains a condensate obtained by condensing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and an amino resin.
It is obtained by subjecting the alkoxysilyl group to a hydrolysis reaction in a reaction raw material solution containing the fluoroalkyl group-containing oligomer and the amino resin.
Composite resin.

(In the formula, R ¹ and R ² each independently indicate −CF (CF ₃ ) − [OCF ₂ CF (CF ₃ )] q-OC ₃ F ₇ groups, and q is an integer of 0 to 10. R ³ , R ⁴ and R ⁵ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. M is an integer of 2 to 3). R ¹ and R ² in the formula of the general formula (1) are -CF (CF ₃ ) -OC ₃ F ₇ units.
The composite resin according to claim 1. The amino resin contains at least one selected from the group consisting of melamine resin, aniline resin, benzoguanamine resin, and urea resin.
The composite resin according to claim 1 or 2. The composite resin is in the form of particles.
The composite resin according to any one of claims 1 to 3. The composite resin according to claim 4, wherein the average particle size of the composite resin is 2000 nm or less. The amino resin in the reaction raw material solution is liquid at 25 ° C. or dissolved in the reaction raw material solution at 25 ° C.
The composite resin according to any one of claims 1 to 5 . The hydrolysis reaction is carried out without a catalyst.
The composite resin according to any one of claims 1 to 6 . The hydrolysis reaction is carried out under an acid catalyst.
The composite resin according to any one of claims 1 to 6 . The hydrolysis reaction is carried out under a base catalyst.
The composite resin according to any one of claims 1 to 6 . A coating material containing the composite resin according to any one of claims 1 to 9 . With the base material
A coating layer containing the composite resin according to any one of claims 1 to 9 provided on the substrate, and a coating layer.
Has a coated substrate. An insulating material containing the composite resin according to any one of claims 1 to 9 . Production of a composite resin comprising a step of hydrolyzing the alkoxysilyl group in a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and an amino resin. Method.

(In the formula, R ¹ and R ² each independently indicate −CF (CF ₃ ) − [OCF ₂ CF (CF ₃ )] q-OC ₃ F ₇ groups, and q is an integer of 0 to 10. R ³ , R ⁴ and R ⁵ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. M is an integer of 2 to 3).