JP2017014466A - Surface control agent for coating material - Google Patents

Abstract

[PROBLEMS] To provide a release agent, a release agent, or an anti-blocking agent without using a silicon raw material and a fluorine raw material, and containing a halogen that is inexpensive and has a high environmental impact, and to form a coating material that is blended with a coating component. Can be formed, and can form a coating film having releasability, releasability, and / or anti-blocking properties, contaminating the furnace used in the thermal curing of the sintering and baking process of the coating film, A surface conditioner for a coating material that does not cause repelling. A surface conditioner for a coating material includes at least one hydrophilic monomer (A) selected from an ether group-containing alkyl (meth) acrylate monomer, an N-vinyl lactam monomer, and a (meth) acrylamide monomer, and an alkyl. The (meth) acrylate monomer (B) is copolymerized and contains a copolymer having a weight average molecular weight of 3000 to 400,000. [Selection figure] None

Description

  The present invention relates to a surface conditioner for a coating material that facilitates peeling of a coating film of the coating material by appropriate adjustment of adhesion, and a coating material containing the same.

  As a method for imparting releasability to the surface of articles such as sticky notes and release films, generally a coating containing a silicone composition such as polysiloxane or a fluorine composition such as a fluororesin such as polytetrafluoroethylene It is known to use materials.

  For example, Patent Document 1 includes a fluorine-containing copolymer and a medium, which are coated or dipped and dried to form a film on the article, thereby imparting adhesiveness and peelability to the surface of the article. A release agent composition that can be used is disclosed.

  Further, in Patent Document 2, a non-crosslinkable fluorine atom-containing organopolysiloxane is blended, and this is applied to the surface of a base material and cured, so that a silicone-based pressure-sensitive adhesive or pressure-sensitive adhesive can be used. A fluorosilicone release agent composition capable of forming a cured film excellent in peelability and peel stability with respect to such an adhesive substance is disclosed.

  Patent Document 3 discloses an addition reaction type solventless type silicone release agent composition that is excellent in thin film coatability and curability by containing polysiloxane.

  Such a silicone-based release agent and fluorine-based release agent, when thermally cured in the baking process of the coating film coated on the base material, decomposed silicone and fluorine products on the surface and low molecular components derived from the raw material. Since they are generated and scattered as foreign substances, the furnace used in the baking process is contaminated and causes problems. Moreover, since the decomposition product of silicone and fluorine has a low polarity, repelling may occur in a coating film obtained by coating a coating material on a base material.

  Furthermore, many fluorine raw materials are relatively expensive and are difficult to use as a release agent raw material for products for the general public such as sticky notes. In addition, because it contains halogen, which has a high environmental load, there are concerns about the impact on the environment, and the use is limited to limited fields.

International Publication No. 2011/099534 Japanese Unexamined Patent Publication No. Hei 6-279682 JP 2007-186804 A

  The present invention has been made to solve the above problems, and does not use a silicone raw material and a fluorine raw material, and is a release agent, a release agent, or an anti-blocking agent without containing an inexpensive halogen with high environmental impact. By using a coating material blended with a coating component, the adhesion can be adjusted, and a coating film having releasability, releasability, and / or anti-blocking properties can be formed, and in the sintering and baking process of the coating film An object of the present invention is to provide a surface conditioner for a coating material that does not contaminate a furnace used in thermosetting or cause repelling of the coating film.

The surface conditioner for a coating material made to achieve the above object has the following chemical formula (I)
^{_{CH 2 = C (R 1)}} COO- (C m H 2m O) n -R 2 ··· (I)
(In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, m is a number of 2 to 4, and n is a number of 1 to 100). Ether group-containing alkyl (meth) acrylate monomer (A1), N-vinyl lactam monomer (A2), and the following chemical formula (II)
^{_{CH 2 = C (R 3)}} CO-N-R 4 R 5 ··· (II)
(In formula (II), R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). At least any hydrophilic monomer (A) selected from (meth) acrylamide monomers (A3);
The following chemical formula (III)
^{_{CH 2 = C (R 6)}} COO-R 7 ··· (III)
(In formula (III), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkyl group having 1 to 30 carbon atoms) and an alkyl (meth) acrylate monomer (B) is copolymerized, It contains a copolymer having a weight average molecular weight of 3000 to 400,000.

  In the surface conditioner for coating material, the copolymer is a copolymer of 10 to 80 parts by mass of the hydrophilic monomer (A) and 20 to 90 parts by mass of the alkyl (meth) acrylate monomer (B). It is preferable.

  In the coating material surface conditioner, the alkyl of the alkyl (meth) acrylate monomer (B) is preferably a branched alkyl group.

  In the coating material surface conditioner, the copolymer preferably has a solubility parameter value determined by a hexane tolerance method of 8.0 to 16.0.

  Similarly, the release agent made to achieve the above object is characterized by comprising the surface conditioner for a coating material.

  Similarly, the release agent made to achieve the above object is characterized by comprising the surface conditioner for a coating material.

  Similarly, the antiblocking agent made to achieve the above object is characterized by comprising the surface conditioner for a coating material.

  Similarly, the coating material made to achieve the above object is characterized in that the surface conditioner for the coating material and a coating component are contained.

  Similarly, the coating film formed to achieve the above-described object is characterized in that the coating material is applied and dried or cured.

  The surface conditioner for a coating material of the present invention can be used by being added in a small amount to the coating material, whereby the coating film of the coating material applied or painted on the substrate can be easily peeled off. In addition, the surface conditioner for coating materials is a release agent that adjusts the adhesion of the substrate surface, a release agent that facilitates removal from the mold when molding rubber or resin, or adhesion between films and sheets. It can be used as an anti-blocking agent that prevents

  This surface conditioner for coating material does not use silicone raw material or fluorine raw material, so when added to the coating material, it contaminates the furnace used in the sintering or baking process of the coating film, or the coating film surface A coating film can be formed without causing repelling. In addition, since it does not contain halogen, which has a high environmental load, it can be used in a wide range without worrying about the impact on the environment. Furthermore, since the material of the surface conditioner for coating material is low cost, it is economically advantageous.

  The coating material of the present invention is provided with functionality such as releasability, releasability, and anti-blocking properties by blending a surface conditioner for the coating material, and a coating film whose adhesion is adjusted. Can be formed.

  The coated film of the present invention can be easily peeled off from a coated or coated substrate, and can easily peel off a protective film and a release film that are in contact with the surface.

  If the surface conditioner for a coating material of the present invention does not require durability, the same usage method as that of a general mold release agent in which only the surface conditioner is directly applied to a substrate can be used.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The surface conditioner for a coating material of the present invention is represented by the ether group-containing alkyl (meth) acrylate monomer (A1), N-vinyllactam monomer (A2) represented by the chemical formula (I), and the chemical formula (II). At least one hydrophilic monomer (A) selected from the (meth) acrylamide monomer (A3) and the alkyl (meth) acrylate monomer (B) represented by the chemical formula (III) are copolymerized at least. It contains a copolymer. This surface conditioner for a coating material is used by being mixed in a small amount with a coating material that is a thermosetting type and / or a heat drying type.

  The weight average molecular weight of the copolymer contained in the coating material surface conditioner is preferably 3000 to 400,000, and more preferably 10,000 to 120,000. If the weight average molecular weight is less than 3000, the compatibility with the coating component is too good when added to the coating material, so it is difficult to orient the molecules of the surface modifier for the coating material on the coating material surface. The peeling effect cannot be obtained. On the other hand, if it exceeds 400,000, the compatibility with the coating material is poor, and as a result, the surface conditioner for coating material causes aggregation, resulting in turbidity in the resulting coating film and impaired appearance.

The ether group-containing alkyl (meth) acrylate monomer (A1) which is the hydrophilic monomer (A) is represented by the following chemical formula (I).
^{_{CH 2 = C (R 1)}} COO- (C m H 2m O) n -R 2 ··· (I)
In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, m is a number of 2 to 4, and n is a number of 1 to 100. Preferably, R ² is the alkyl group and n is 1-30.

  As the ether group-containing alkyl (meth) acrylate monomer (A1), specifically, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid polyethylene glycol (ethylene glycol polymerization number 2-100) ester , (Meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid polypropylene glycol (propylene glycol polymerization number 2-100) ester, (meth) acrylic acid poly (ethylene-propylene) glycol (ethylene glycol-propylene) Glycol polymerization number 2-100) ester, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid polytetramethylene glycol (tetramethylene glycol polymerization number 2-100) ester, (meth) Acrylic acid poly Ethylene-tetramethylene) glycol (ethylene glycol-tetramethylene glycol polymerization number 2-100) ester, (meth) acrylic acid poly (propylene-tetramethylene) glycol (propylene glycol-tetramethylene glycol polymerization number 2-100) ) Ester, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid methoxypolyethylene glycol (ethylene glycol polymerization number 2-100) ester, (meth) acrylic acid-n-methoxypropyl, ( (Meth) acrylic acid methoxypolypropylene glycol (with propylene glycol polymerization number 2 to 100) ester, (meth) acrylic acid methoxypoly (ethylene-propylene) glycol (ethylene glycol-propylene glycol) (Meth) acrylic acid-n-methoxybutyl, (meth) acrylic acid methoxy polytetramethylene glycol (tetramethylene glycol polymerization number 2-100) ester, (meth) acrylic Acid methoxy poly (ethylene-tetramethylene) glycol (ethylene glycol-tetramethylene glycol polymerization number 2-100) ester, (meth) acrylic acid methoxy poly (propylene-tetramethylene) glycol (propylene glycol-tetramethylene glycol polymerization number) 2 to 100) ester, (meth) acrylic acid-n-propoxyethyl, (meth) acrylic acid-isopropoxyethyl, (meth) acrylic acid propoxypolyethylene glycol (ethylene glycol polymerization number 2 to 100) ) Ester, propoxypropyl (meth) acrylate, propoxypolypropylene glycol (meth) acrylate (with propylene glycol polymerization number 2 to 100) ester, propoxypoly (ethylene-propylene) glycol (ethylene) (meth) acrylate Glycol-propylene glycol polymerization number 2-100) ester, (meth) acrylic acid propoxybutyl, (meth) acrylic acid propoxypolytetramethylene glycol (tetramethylene glycol polymerization number 2-100) ester, (meta ) Propoxy poly (ethylene-tetramethylene) glycol acrylate (ethylene glycol-tetramethylene glycol polymerization number 2-100) ester, (meth) acrylic propoxy poly (propylene-teto) Methylene) glycol (propylene glycol-tetramethylene glycol having a polymerization number of 2 to 100) ester, (meth) acrylic acid-2-butoxyethyl, (meth) acrylic acid-iso-butoxyethyl, (meth) acrylic acid-tert -Butoxyethyl, (meth) acrylic acid butoxypolyethylene glycol (ethylene glycol polymerization number 2 to 100) ester, (meth) acrylic acid butoxypropyl, (meth) acrylic acid butoxypolypropylene glycol (propylene glycol polymerization number 2 100) ester, (meth) acrylic acid butoxy poly (ethylene-propylene) glycol (ethylene glycol-propylene glycol polymerization number 2-100) ester, (meth) butoxybutyl acrylate, (meta Butoxypolytetramethylene glycol acrylate (having a tetramethylene glycol polymerization number of 2 to 100) ester, (meth) acrylic acid butoxypoly (ethylene-tetramethylene) glycol (having an ethylene glycol-tetramethylene glycol polymerization number of 2 to 100) ) Ester, (meth) acrylic acid butoxy poly (propylene-tetramethylene) glycol (propylene glycol-tetramethylene glycol polymerization number 2-100) ester, (meth) acrylic acid octoxy poly (ethylene-propylene) glycol (ethylene glycol-) (Propylene glycol polymerization number 2-100) ester, (meth) acrylic acid lauroxypolyethylene glycol (ethylene glycol polymerization number 2-100) ester, (meth) A) Ether group such as stearoxypolyethylene glycol acrylate (ethylene glycol polymerization number 2 to 100) ester, (meth) acrylic acid phenoxypolyethylene glycol (ethylene glycol polymerization number 2 to 100) ester Examples include alkyl (meth) acrylates. These may be used alone or in combination.

  Specific examples of the N-vinyllactam monomer (A2) that is the hydrophilic monomer (A) include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyl-4-butylpyrrolidone, N-vinyl- 4-propylpyrrolidone, N-vinyl-4-ethylpyrrolidone, N-vinyl-4-methylpyrrolidone, N-vinyl-4-methyl-5-ethylpyrrolidone, N-vinyl-4-methyl-5-propylpyrrolidone, N -Vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-5-propylpyrrolidone, N-vinyl-5-butylpyrrolidone, N-vinyl-4-methylcaprolactam, N-vinyl-6-methylcaprolactam, N- Examples thereof include vinyl-6-propylcaprolactam and N-vinyl-7-butylcaprolactam. These may be used alone or in combination.

The (meth) acrylamide monomer (A3) which is the hydrophilic monomer (A) is represented by the following chemical formula (II).
^{_{CH 2 = C (R 3)}} CO-N-R 4 R 5 ··· (II)
In formula (II), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  Specific examples of the (meth) acrylamide monomer (A3) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl ( (Meth) acrylamide, N-cyclopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl-N-methylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropyl Examples include acrylamide, N, N-diethyl (meth) acrylamide, N-ethyl-N-propyl acrylamide, N, N-di-n-propyl (meth) acrylamide, and N, N-diisopropyl (meth) acrylamide. These may be used alone or in combination.

The alkyl (meth) acrylate monomer (B) is represented by the following chemical formula (III).
^{_{CH 2 = C (R 6)}} COO-R 7 ··· (III)
In formula (III), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. The alkyl chain of the alkyl (meth) acrylate monomer (B) can exhibit the desired characteristics regardless of whether it is linear or branched. Preferably it is.

  As the alkyl (meth) acrylate monomer (B), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-, or iso-propyl (meth) acrylate, n-, iso-, sec-, or tert-butyl (meth) acrylate, n-amyl (meth) acrylate, sec-amyl (meth) acrylate, iso-amyl (meth) acrylate, tert-amyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) Acrylate, isohexyl (meth) acrylate, heptyl (meth) acrylate, isoheptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate , Isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, isoundecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (Meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate. These may be used alone or in combination.

  The copolymer contained in the coating material surface conditioner is a copolymer of 10 to 80 parts by mass of the hydrophilic monomer (A) and 20 to 90 parts by mass of the alkyl (meth) acrylate monomer (B). It is preferable. More preferably, 40 to 70 parts by mass of the hydrophilic monomer (A) and 30 to 60 parts by mass of the alkyl (meth) acrylate monomer (B) are copolymerized.

  When the hydrophilic monomer (A) is 10 to 80 parts by mass, when it is added to the coating material, it is properly compatible, and when the coating film is formed, the release property is achieved by orienting the coating film surface. Can be improved. When the hydrophilic monomer (A) is less than 10 parts by mass, for example, the ether group-containing alkyl (meth) acrylate monomer (A1) represented by the chemical formula (I) in the copolymer and an N-vinyl lactam monomer ( A2) and a surface conditioner for a coating material that is not applied to the present application, including a copolymer that does not contain any structure derived from the (meth) acrylamide monomer (A3) represented by the chemical formula (III), Since the copolymer has the same low polarity and poor compatibility with the coating material, the surface conditioner for the coating material is agglomerated, resulting in turbidity in the resulting coating film and impaired appearance. . In addition, when the hydrophilic monomer (A) exceeds 80 parts by mass, the ion-exchanged water dissolves indefinitely when measuring the solubility parameter (SP value) of the copolymer to be described later by the hexane tolerance method. It becomes impossible to measure the SP value.

  On the other hand, when the alkyl (meth) acrylate monomer (B) is less than 20 parts by mass, ion-exchanged water dissolves indefinitely when measuring the SP value of the copolymer by the hexane tolerance method, as described above. Thus, accurate SP value measurement becomes impossible. Moreover, when the alkyl (meth) acrylate monomer (B) exceeds 90 parts by mass, the polarity of the copolymer is lowered, the compatibility with the coating material is poor, and the surface conditioner for the coating material is agglomerated as described above. As a result, the coating film obtained becomes turbid and the appearance is impaired.

  The SP value is used as a method for representing the polarity of the copolymer contained in the surface conditioner for a coating material. The SP value can be estimated from the molecular structure, and various methods have been proposed. Here, the hexane tolerance method for determining the midpoint of the solvent-soluble range is used. The calculation method of SP value by the hexane tolerance method is a well-known method. Two resin solids dissolved in tetrahydrofuran (THF) are prepared, and ion-exchanged water is dropped into one of the resin solutions. One is calculated from the drop volume of ion-exchanged water and normal hexane in which normal hexane is dropped and the resin solution becomes cloudy.

  The SP value of the copolymer is preferably 8.0 to 16.0, and more preferably 10.0 to 13.0. If the SP value of the copolymer is less than 8.0, the solubility in the solvent will be poor, and the copolymer will precipitate during the polymerization reaction, making it difficult to produce, or even if it can be produced, the solubility is too bad. For this reason, the copolymer may aggregate and impair the appearance of the coating film. If the SP value of the copolymer exceeds 16.0, the coating film formed using the copolymer is too compatible with the coating liquid and the copolymer is not oriented on the surface. A sufficient peeling effect cannot be obtained.

  The copolymer contained in the coating material surface conditioner is copolymerized with a hydrophilic monomer (A) and an alkyl (meth) acrylate monomer (B), as well as a different monomer (C). It may be a thing.

  The monomer (C) is not particularly limited as long as it is a copolymerizable unsaturated monomer other than the hydrophilic monomer (A) and the alkyl (meth) acrylate monomer (B). Examples of the monomer (C) include (meth) acrylic acid which is acrylic acid or methacrylic acid; (meth) acrylic acid hydroxyalkyl ester, acrylic acid benzyl ester, polycaprolactone-modified hydroxyalkyl acrylic acid ester or methacrylic acid ester; styrene , Α-methylstyrene, chlorostyrene, aromatic hydrocarbon vinyl compounds such as vinyltoluene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether and dodecyl vinyl ether; diallyl phthalate Allylic compounds such as vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, and aliphatic hydrocarbon vinyl compounds such as fluoroolefin maleimide. . These may be used alone or in combination. In the copolymer, the total of the hydrophilic monomer (A) and the alkyl (meth) acrylate monomer (B) and the monomer (C) are preferably 100: 1 to 30 by mass ratio.

  The surface conditioner for a coating material of the present invention may be composed only of these copolymers, or may be those obtained by dissolving or suspending these copolymers in an inert solvent.

  The inert solvent can dissolve or suspend the copolymer and is preferably miscible with the coating material. Specific examples of the inert solvent include hydrocarbon solvents such as xylene, toluene, and cyclohexane, ketone solvents such as cyclohexanone and methyl isobutyl ketone, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, carbitol, and butyl. Ether solvents such as carbitol, diethyl carbitol, propylene glycol monomethyl ether, normal butyl acetate, isobutyl acetate, normal amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, ester solvents such as 3-methoxybutyl acetate, Normal butyl alcohol, secondary butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-methoxybutane They include alcohol solvents such as Lumpur. These inert solvents may be used alone or in combination.

  One preparation example of the surface conditioner for a coating material of the present invention is shown below.

  From the ether group-containing alkyl (meth) acrylate monomer (A1) represented by the chemical formula (I), the N-vinyl lactam monomer (A2), and the (meth) acrylamide monomer (A3) represented by the chemical formula (II). At least one of the selected hydrophilic monomers (A) and the alkyl (meth) acrylate monomer (B) are mixed, and if necessary, the monomer (C) is mixed to obtain a polymerization initiator, and further as required. Accordingly, polymerization is carried out in a solvent in the presence of a chain transfer agent to obtain a copolymer. By mixing the obtained copolymer and, if necessary, an inert solvent, a surface conditioner for a coating material in which the copolymer is dissolved or suspended in the inert solvent can be prepared.

  The obtained copolymer may be a random copolymer, a block copolymer, or a graft copolymer.

  Examples of the polymerization method include radical copolymerization and anion copolymerization.

  As the solvent used in the polymerization reaction, the same solvents as those exemplified for the inert solvent for dissolving or suspending the copolymer after synthesis can be exemplified, and can be appropriately selected from these solvents and used. .

  The polymerization initiator used for the polymerization reaction is appropriately selected according to the type of polymerization reaction to be used. Examples of radical polymerization initiators include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, tert-hexylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2 , 5-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butyl Peroxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butyl Luperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethyl Peroxide polymerization initiators such as butylperoxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate; 2,2-azobis ( Isovaleronitrile), 2,2-azobis (isobutyronitrile), 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 1,1- Azobis (1-cyclohexanecarbonitrile), dimethyl-2,2-azobisisobutyrate, 4,4-azobis (4-cyanovaleric acid), 1,1 Azobis (1-acetoxy-1-phenylethane), 2,2-azobis (2-methylbutyramide), 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis ( 2-methylamidinopropane) dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane], 2,2-azobis [2-methyl-N- (2-hydroxyethyl) propionamide 2,2-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2-azobis (N-butyl-2-methylpropionamide), 2,2-azobis An azo polymerization initiator such as (N-cyclohexyl-2-methylpropionamide) may be mentioned. These polymerization initiators may be used alone or in combination.

  The chain transfer agent used for the polymerization reaction is appropriately selected according to the type of polymerization reaction to be used. Examples of chain transfer agents include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, n-butyl mercaptan; carbon tetrachloride, ethylene bromide. And halogen compounds such as α-methylstyrene dimer. These chain transfer agents may be used alone or in combination.

  The obtained surface conditioner for a coating material can be used as a release agent, a release agent, and / or an antiblocking agent between two different substrates. Although it does not specifically limit as a base material, For example, a nonwoven fabric, resin, paper, leather, a metal, concrete, gypsum, glass etc. are mentioned. Examples of the combination of these two different base materials include resin and metal, paper and fiber, and the like. Specifically, it can be used as a release film for an electronic substrate, a protective material for a pressure-sensitive adhesive sheet or a pressure-sensitive adhesive surface of a tape, and the like.

  In addition, this surface conditioner for a coating material becomes a coating material imparted with peelability, releasability and / or antiblocking property by being blended in a small amount with a coating component forming a film.

  The coating material of the present invention is blended with a surface conditioner for a coating material, and exhibits release properties, release properties, and / or anti-blocking properties, and selectively leveling properties, antifouling properties, and base materials. The wettability of can be improved.

  This coating material can be prepared by mixing the surface conditioner for coating material and the coating component simultaneously or in any order. For example, it is possible to obtain a coating material to which releasability is imparted by blending and kneading a surface conditioner for a coating material with a coating component mixed in advance.

  In this coating material, it is preferable that the surface conditioner for coating material is blended in an amount of 0.01 to 5% by mass in terms of solid content with respect to the total amount of the coating material. It is even more preferable that 0.05 to 1% by mass is blended.

  Although a coating component is not specifically limited, For example, colorants, such as a pigment and dye, resin, a diluent solvent, a catalyst, and surfactant are mentioned.

  In the coating material, a sensitizer, an antistatic agent, a leveling agent, a substrate wetting agent, a repellency inhibitor, a dispersant, and a viscosity modifier may be blended as necessary.

  In the coating component, a thermosetting coating material can be obtained by containing a resin that promotes a crosslinking reaction and forms a cured film by increasing the temperature. This resin component includes thermosetting properties such as acrylic melamine cured paints, polyester melamine cured paints, acid epoxy cured paints, and acrylic urethane and polyester urethane cured paints that react with hydroxyl groups and isocyanates. Any material containing resin may be used. In addition, when the coating component contains, for example, nitrocellulose lacquer or acrylic lacquer, a heat-drying type coating material that forms a film by drying the solvent by heat treatment can be obtained.

  The dilution solvent as the coating component is not particularly limited as long as it is a commonly used organic solvent. Examples of the diluent solvent include hydrocarbon solvents such as xylene, toluene, and cyclohexane; ketone solvents such as cyclohexanone and methyl isobutyl ketone; cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, Ether solvents such as diethyl carbitol and propylene glycol monomethyl ether; normal solvents such as normal butyl acetate, isobutyl acetate, normal amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; normal butyl alcohol Secondary butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-methoxybutanol Include alcohol solvents such as. These solvents may be used alone or in combination, and may be used by mixing with water.

  Such a coating material can form a coating film whose adhesion is adjusted by coating the substrate exemplified above and drying or curing. The obtained coating film can impart appropriate peelability to the surface of the substrate, and is excellent in durability and texture.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

  Examples of synthesizing a copolymer to which the present invention is applied and preparing a surface conditioner for a coating material are shown in Synthesis Examples 1 to 6, and examples of synthesizing an unapplicable copolymer and preparing a surface conditioner for a coating material The results are shown in Comparative Synthesis Examples 1-6.

(Synthesis Example 1)
100 parts by mass of octanol was added to a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the temperature was raised to 100 ° C. in a nitrogen gas atmosphere. The temperature of the octanol was maintained at 100 ° C., and the dropping solution (a-1) shown in Table 1 below was dropped at a constant rate over 2 hours with a dropping funnel to synthesize a monomer solution. After completion of the dropping, the monomer solution was heated to 115 ° C. and reacted for 2 hours to synthesize a copolymer. Then, it diluted with octanol so that a residue might be 50%, and obtained the surface conditioner for coating materials containing a copolymer. The gel permeation chromatography that can separate molecules with different molecular weights (column: TSKgelSuperMultiporeHZ-M (manufactured by Tosoh Corporation), elution solvent: THF) is used to elute the copolymer in the surface conditioner for coating materials for each molecular weight, The molecular weight distribution was determined. A calibration curve was previously obtained from a polystyrene standard substance having a known molecular weight, and the weight average molecular weight of the copolymer was determined by comparison with the molecular weight distribution of the copolymer in the surface conditioner for a coating material. As a result, the weight average molecular weight of the copolymer in the surface conditioner for coating material was 50000 in terms of polystyrene. The solubility parameter value determined by the hexane tolerance method was 11.5.

(Synthesis Example 2)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dropping solution in Synthesis Example 1 was changed to (а-2) and the dropping temperature was changed to 90 ° C. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 120,000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 10.0.

(Synthesis Example 3)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dropping solution in Synthesis Example 1 was changed to (а-3) and the dropping temperature was changed to 110 ° C. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 5000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 12.0.

(Synthesis Example 4)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dripping solution in Synthesis Example 1 was changed to (а-4). The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 50000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 10.5.

(Synthesis Example 5)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dripping solution in Synthesis Example 1 was changed to (а-5). The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 50000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 13.0.

(Synthesis Example 6)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dripping solution in Synthesis Example 1 was changed to (а-6). The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 50000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 11.5.

(Comparative Synthesis Example 1)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dropping solution in Synthesis Example 1 was changed to (b-1) in Table 2 below. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 50000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 11.0.

(Comparative Synthesis Example 2)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dropping solution in Synthesis Example 1 was changed to (b-2) in Table 2 below. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 50000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 10.0.

(Comparative Synthesis Example 3)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dripping solution in Synthesis Example 1 was changed to (b-3) in Table 2 below and the dripping temperature was changed to 120 ° C. It was. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 2000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 12.0.

(Comparative Synthesis Example 4)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dropping solution in Synthesis Example 1 was changed to (b-4) in Table 2 below and the dropping temperature was changed to 90 ° C. It was. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 150,000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 7.5.

(Comparative Synthesis Example 5)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dripping solution in Synthesis Example 1 was changed to (b-5) in Table 2 below and the dripping temperature was changed to 110 ° C. It was. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 5000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 16.5.

(Comparative Synthesis Example 6)
A surface conditioner for a coating material was obtained in the same manner as in Synthesis Example 1 except that the dropping solution in Synthesis Example 1 was changed to (b-6) in Table 2 below. The weight average molecular weight calculated | required by the method similar to the synthesis example 1 about the copolymer in the surface modifier for this coating material was 50000 in polystyrene conversion. The solubility parameter value determined by the hexane tolerance method was 12.0.

  Table 1 shows the unit as a mass part with respect to the blending amount of each component for each dropping solution used in Synthesis Examples 1-6. Table 2 shows the unit as a part by mass with respect to the blending amount of each component for each dropping solution used in Comparative Synthesis Examples 1-6. In Tables 1 and 2, ether group-containing alkyl (meth) acrylate monomer (A1) is monomer (A1), N-vinyl lactam monomer (A2) is monomer (A2), and (meth) acrylamide monomer (A3) is a monomer. As (A3), the alkyl (meth) acrylate monomer (B) is also shown as the monomer (B). Furthermore, the monomer (A), the monomer (B), and the monomer (C) other than the monomer (D) are shown.

  Examples of preparing coating materials and coating films to which the present invention is applied using the surface conditioners for coating materials of Synthesis Examples 1 to 6 are shown in Examples 1 to 6, and the surfaces for coating materials of Comparative Synthesis Examples 1 to 6 Comparative Examples 1 to 6 show examples in which a coating material and a coating film in which the present invention is not applied are prepared using a regulator.

Example 1
100 parts by mass of urethane acrylate UA-306I (product name of Kyoeisha Chemical Co., Ltd.), 40 parts by mass of methyl ethyl ketone, and photopolymerization initiator Irgacure 184 (product name of Ciba Japan Co., Ltd .; Irgacure is Ciba Japan Co., Ltd.) 3 parts by mass of registered trademark of Co., Ltd. and 0.6 parts by mass of the surface conditioner for coating material of Synthesis Example 1 were kneaded at 1000 rpm for 2 minutes using a lab disper to prepare an ultraviolet curable coating material did. This coating material is applied to a polyethylene terephthalate (PET) film, dried at 80 ° C. for 1 minute, and then activated energy of 600 mJ / cm ² using an 80 W high pressure mercury lamp active energy irradiation device (product of Nippon Battery Co., Ltd.). Was irradiated at a distance of 10 cm from the substrate to obtain a cured coating film.

(Examples 2-6, Comparative Examples 1-6)
Example 2 in the same manner as in Example 1 except that the surface conditioner for coating material in Example 1 was changed to the surface conditioner for coating material in Synthesis Examples 2-6 and Comparative Synthesis Examples 1-6. -6, and the ultraviolet curable coating material of Comparative Examples 1-6, and the coating film were prepared.

  The physicochemical tests of the following compatibility test and adhesion test were performed on the ultraviolet curable coating materials obtained in Examples 1 to 6 and Comparative Examples 1 to 6 and these coating films.

(Compatibility test)
A compatibility test measures the transmittance | permeability of the ultraviolet curable coating material obtained in Examples 1-6 and Comparative Examples 1-6, and evaluates the compatibility of the copolymer in a coating material from the transparency. That's it. The transmittance obtained with a spectrocolorimeter (haze meter CM-3600 (manufactured by Konica Minolta Optics, Inc.)) was 100% when no additive was added, and the transmittance was 95 compared to that. Evaluation was made in three stages, with ◯ for% or more, Δ for a transmittance of 90-95%, and X for a transmittance of less than 90%.

(Adhesion test)
In the adhesion test, the ultraviolet curable coating materials obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were applied with a No. 22 bar coater and cured by the method described in Example 1 to obtain a coating film. It was. The coating film was cut and peeled off after applying a transparent pressure-sensitive adhesive tape, and the adhesion was evaluated by visually checking the degree of peeling. The evaluation was made in three stages, with ◯ when the coating film was completely peeled off, Δ when the coating film remained even partly, and x when peeling did not occur at all.

  The results are summarized in Table 3. As is clear from Table 3, the ultraviolet curable coating materials of Examples 1 to 6 were excellent in compatibility. Moreover, the coating film surface which applied this ultraviolet curable coating material was excellent in adhesiveness. On the other hand, as for the ultraviolet curable coating material of Comparative Examples 1-6, any item was inadequate compared with the ultraviolet curable coating material of Examples 1-6.

  The surface conditioner for a coating material according to the present invention is used as a release agent, a release agent, or an anti-blocking agent, and a small amount is added to the coating material in order to impart functions such as a release property, a release property, and an anti-blocking property. Used in combination. The coating material to which the surface conditioner for coating material is added is useful for forming a coating film with adjusted adhesion.

Claims (9)

The following chemical formula (I)
^{_{CH 2 = C (R 1)}} COO- (C m H 2m O) n -R 2 ··· (I)
(In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, m is a number of 2 to 4, and n is a number of 1 to 100). Ether group-containing alkyl (meth) acrylate monomer (A1), N-vinyl lactam monomer (A2), and the following chemical formula (II)
^{_{CH 2 = C (R 3)}} CO-N-R 4 R 5 ··· (II)
(In formula (II), R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). At least any hydrophilic monomer (A) selected from (meth) acrylamide monomers (A3);
The following chemical formula (III)
^{_{CH 2 = C (R 6)}} COO-R 7 ··· (III)
(In formula (III), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkyl group having 1 to 30 carbon atoms) and an alkyl (meth) acrylate monomer (B) is copolymerized, A surface conditioner for a coating material, comprising a copolymer having a weight average molecular weight of 3000 to 400,000.   The copolymer is a copolymer of 10 to 80 parts by mass of the hydrophilic monomer (A) and 20 to 90 parts by mass of the alkyl (meth) acrylate monomer (B). Item 11. A surface conditioner for a coating material according to Item 1.   The surface conditioning agent for a coating material according to claim 1, wherein the alkyl of the alkyl (meth) acrylate monomer (B) is a branched alkyl group.   The surface conditioning agent for a coating material according to claim 1, wherein the copolymer has a solubility parameter value determined by a hexane tolerance method of 8.0 to 16.0.   A release agent comprising the surface conditioner for a coating material according to claim 1.   A mold release agent comprising the surface conditioner for a coating material according to claim 1.   An antiblocking agent comprising the surface conditioner for a coating material according to claim 1.   A coating material comprising the surface conditioner for a coating material according to claim 1 and a coating component.   A coating film, wherein the coating material according to claim 8 is painted and dried or cured.