WO2017158643A1

WO2017158643A1 - Primer composition, laminated member, and method for producing primer composition

Info

Publication number: WO2017158643A1
Application number: PCT/JP2016/001523
Authority: WO
Inventors: 輝榊原; 前田　浩司; 伸哉駒引
Original assignee: 互応化学工業株式会社
Priority date: 2016-03-16
Filing date: 2016-03-16
Publication date: 2017-09-21
Also published as: CN106715611A; KR20170118677A; TWI660012B; CN106715611B; JPWO2017158643A1; TW201734156A; JP6055578B1; KR101825454B1

Abstract

Provided is a primer composition with which a highly adhesive and transparent primer layer can be formed by applying the composition to a substrate. The primer composition includes a polymerized reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The polymerized reaction product (A) is a product produced by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and the ethylenically unsaturated monomer (b). The saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH/g. The ethylenically unsaturated monomer (b) includes a nonionic ethylenically unsaturated monomer (b1).

Description

Primer composition, laminated member, and method for producing primer composition

The present invention relates to a primer composition, a laminated member, and a method for producing a primer composition, and more specifically, a primer composition for forming a primer layer, a laminated member provided with a primer layer formed from the primer composition, and this The present invention relates to a method for producing a primer composition.

Various substrates, for example, films made of polyolefin resin such as polypropylene and polyethylene, may be coated, provided with ink for printing, or provided with a metal vapor deposition layer for providing gas barrier properties. . When the adhesion between the substrate and the coating film, ink, metal, etc. is low, such as when the substrate does not have a polar group, corona discharge, plasma treatment, flame treatment, ultraviolet irradiation treatment on the substrate, Surface treatment such as solvent treatment may be performed.

However, there is a problem that these surface treatments include dangerous work. Further, there is a problem that the adhesiveness improved by the surface treatment tends to decrease with time.

Therefore, conventionally, in order to improve the adhesion of the substrate, a primer having excellent adhesion is applied to the substrate.

As such a primer, for example, Patent Document 1 discloses a group consisting of an unsaturated compound having a hydroxyl group, an unsaturated carboxylic acid ester, styrene, an unsaturated carboxylic acid, an unsaturated hydrocarbon, a vinyl ester, and a vinyl halide. A main agent (A) composed of a copolymer having one or more unsaturated compounds as monomers, a curing agent (B) composed of a compound having an isocyanate group, and two or more carboxylic acid groups in one molecule Alternatively, a primer containing the compound (C) having one or more carboxylic anhydride groups is disclosed.

Primers may be required to have high transparency as well as high adhesion. For example, when painting is applied only to a part of the surface of the substrate, and when coating with high transparency is applied to the substrate, the primer layer formed from the primer is required to have high transparency. Sometimes.

International Publication WO2010 / 038643

An object of the present invention is to provide a primer composition capable of forming a primer layer having high adhesiveness and transparency by being applied to a substrate, a laminated member including a primer layer formed from the primer composition, and the primer It is to provide a method for producing a composition.

The primer composition according to one embodiment of the present invention contains a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The polymerization reaction product (A) emulsion-polymerizes the ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b). It is a product produced by The saturated polyester resin (a) has an acid value within the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

The method for producing a primer composition according to one embodiment of the present invention is a method for producing a primer composition containing a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). This primer composition is produced by emulsion polymerization of the ethylenically unsaturated monomer (b) in a mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b). Synthesizing the polymerization reaction product (A) and mixing the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B). The saturated polyester resin (a) has an acid value within the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

According to one aspect of the present invention, a primer composition capable of forming a primer layer having high adhesion and transparency by being applied to a substrate, a laminated member including a primer layer formed from the primer composition, And the manufacturing method of this primer composition can be obtained.

It is sectional drawing which shows the laminated member in one Embodiment of this invention.

The primer composition according to this embodiment is used for obtaining a laminated member 1 as shown in FIG. The laminated member 1 includes a base material 2, a primer layer 3 on the base material 2 containing a dried product of the primer composition, and a metal or resin outer layer 4 on the primer layer 3.

The primer composition contains a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The polymerization reaction product (A) is produced by emulsion polymerization of the ethylenically unsaturated monomer (b) in the mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b). Product. The saturated polyester resin (a) has an acid value within the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

The primer layer 3 can be formed on the substrate 2 by applying the primer composition onto the substrate 2 and drying it. The primer layer 3 can have high adhesiveness with the base material 2 even if the base material 2 is a film made of polyolefin resin such as polypropylene or polyethylene. Adhesiveness of the primer layer 3 to the substrate 2 is realized particularly by the maleic acid-modified polyolefin resin (B). Further, when the resin or metal outer layer 4 is formed on the primer layer 3, the primer layer 3 can have high adhesiveness with the outer layer 4. High adhesion between the primer layer 3 and the outer layer 4 is realized particularly by the polymerization reaction product (A).

Furthermore, the polymerization reaction product is obtained by emulsion polymerization of the ethylenically unsaturated monomer (b) in the mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) as described above. When (A) is generated, the primer layer 3 can have high transparency.

The polymerization reaction product (A) is presumed to be a mixture of an emulsion polymer of a saturated polyester resin (a) and an ethylenically unsaturated monomer (b).

However, in this embodiment, the saturated polyester resin (a) and the emulsion polymer of the ethylenically unsaturated monomer (b) are not simply mixed, but the polymerization reaction product (A) is generated by the above method. There is a special feature. During the emulsion polymerization of the ethylenically unsaturated monomer (b), the saturated polyester resin (a) can serve as an emulsifier. For this reason, in this embodiment, the polymerization reaction product (A) can contribute to improving the transparency of the primer layer 3 and can also contribute to improving the adhesion between the primer layer 3 and the outer layer 4.

Furthermore, since no emulsifier other than the saturated polyester resin (a) is required at the time of emulsion polymerization, it is possible to prevent the primer composition from containing an emulsifier other than the saturated polyester resin (a). When the primer composition does not contain an emulsifier other than the saturated polyester resin (a), deterioration of the appearance and performance of the primer layer 3 due to bleeding out of the emulsifier from the primer layer 3 is suppressed.

In addition, a polymer is synthesized by emulsion polymerization of the ethylenically unsaturated monomer (b) using an emulsifier other than the saturated polyester resin (a), and the polymer is synthesized with the saturated polyester resin (a) and maleic acid. When mixing with modified polyolefin resin (B) and water (C) and preparing a composition, the transparency of the layer formed from this composition is inferior to the transparency of the primer layer 3 which concerns on this embodiment. Furthermore, the adhesion between the layer formed from this composition and the outer layer 4 is inferior to the adhesion of the primer layer 3 according to this embodiment. That is, the composition and layer described above are different from the primer composition and primer layer 3 according to this embodiment. However, even when the inventor analyzed both by the infrared absorption method and the high performance liquid chromatography method, no significant difference was found between the analysis results of both. Therefore, the structure or characteristics of the polymerization reaction product (A) cannot be specified in terms of words.

The components of the primer composition will be described in more detail.

The saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2).

The polyvalent carboxylic acid residue (a1) includes, for example, a trivalent or higher polyvalent carboxylic acid residue (a11), a polyvalent carboxylic acid residue (a12) having a metal sulfonate group, and other dicarboxylic acid residues ( at least one group selected from the group consisting of a13).

Examples of the trivalent or higher polyvalent carboxylic acid residue (a11) include hemimellitic acid residue, trimellitic acid residue, trimedic acid residue, merophanic acid residue, pyromellitic acid residue, and benzenepentacarboxylic acid residue. , Meritic acid residue, cyclopropane-1,2,3-tricarboxylic acid residue, cyclopentane-1,2,3,4-tetracarboxylic acid residue, and ethanetetracarboxylic acid residue. Containing at least one kind of group.

The polyvalent carboxylic acid residue (a12) having a metal sulfonate group is, for example, a dicarboxylic acid residue having a metal sulfonate group. More specifically, the polyvalent carboxylic acid residue (a12) is, for example, a 5-sulfoisophthalic acid residue, a 2-sulfoisophthalic acid residue, a 4-sulfoisophthalic acid residue, a 2-sulfoterephthalic acid residue, And at least one group selected from the group consisting of 4-sulfonaphthalene-2,6-dicarboxylic acid residues.

The dicarboxylic acid residue (a13) contains, for example, at least one of an aromatic dicarboxylic acid residue and an aliphatic dicarboxylic acid residue. Aromatic dicarboxylic acid residues include, for example, terephthalic acid residues, isophthalic acid residues, phthalic acid residues, diphenic acid residues, naphthalic acid residues, 1,2-naphthalenedicarboxylic acid residues, 1,4-naphthalenedicarboxylic acid It contains at least one group selected from the group consisting of acid residues, 1,5-naphthalenedicarboxylic acid residues, and 2,6-naphthalenedicarboxylic acid residues. Aliphatic dicarboxylic acid residues include, for example, linear, branched and alicyclic oxalic acid residues, malonic acid residues, succinic acid residues, maleic acid residues, itaconic acid residues, glutaric acid residues, adipic acid Residue, pimelic acid residue, 2,2-dimethylglutaric acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, dodecanedioic acid residue, 1,3-cyclopentanedicarboxylic acid residue 1,4-cyclohexanedicarboxylic acid residue, 1,3-cyclohexanedicarboxylic acid residue, 1,2-cyclohexanedicarboxylic acid residue, 1,2-cyclopropanedicarboxylic acid residue, 1,2-cyclobutanedicarboxylic acid residue It contains at least one group selected from the group consisting of a group, a diglycolic acid residue, and a thiodipropionic acid residue. Terephthalic acid residue, isophthalic acid residue and 2,6-naphthalenedicarboxylic acid residue among aromatic dicarboxylic acid residues, and succinic acid residue, adipic acid residue, sebacin among aliphatic dicarboxylic acid residues The acid residue, dodecanedioic acid residue, and 1,4-cyclohexanedicarboxylic acid residue are preferable from the viewpoints of easiness of reaction, adhesion of the resulting resin, weather resistance, durability, and the like. In particular, the aromatic dicarboxylic acid residue and the 1,4-cyclohexanedicarboxylic acid residue are preferably the main components of the polyvalent carboxylic acid residue (a1).

The polyvalent carboxylic acid residue (a1) preferably contains a trivalent or higher polyvalent carboxylic acid residue (a11). In this case, the saturated polyester resin (a) may have a carboxyl group derived from a trivalent or higher polyvalent carboxylic acid residue (a11). Therefore, the saturated polyester resin (a) can effectively function as an emulsifier, and the saturated polyester resin (a) can have high water solubility or water dispersibility. Furthermore, the saturated polyester resin (a) can impart high adhesion to the base layer 2 and the outer layer 4 to the primer layer 3.

The amount of the polycarboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is preferably in the range of 1 to 50 mol%. When the amount of the polycarboxylic acid residue (a11) is in the range of 1 to 50 mol%, the saturated polyester resin (a) functions particularly effectively as an emulsifier, and the saturated polyester resin (a) is particularly effective. It has high water solubility or water dispersibility, and the saturated polyester resin (a) can impart particularly high adhesion to the primer layer 3. The amount of the polyvalent carboxylic acid residue (a11) is more preferably 5 mol% or more, and even more preferably 10 mol% or more. Further, the amount of the polycarboxylic acid residue (a11) is more preferably 45 mol% or less, and further preferably 40 mol% or less.

The polyvalent carboxylic acid residue (a1) may contain a polyvalent carboxylic acid residue (a12) having a metal sulfonate group. In this case, the saturated polyester resin (a) may have a metal sulfonate group that is a polar group derived from the polyvalent carboxylic acid residue (a12). For this reason, the saturated polyester resin (a) has particularly high water solubility or water dispersibility, and the polymerization reaction product (A) can impart particularly high adhesion to the primer layer 3.

However, in order to impart high water resistance to the primer layer 3, the amount of the polyvalent carboxylic acid residue (a12) relative to the polyvalent carboxylic acid residue (a1) is preferably 3 mol% or less, If it is 1 mol% or less, it is more preferable.

It is also preferred that the polyvalent carboxylic acid residue (a1) contains an alicyclic polyvalent carboxylic acid residue (a10). In this case, the primer layer 3 can have particularly high transparency.

Examples of the alicyclic polyvalent carboxylic acid residue (a10) include 1,4-cyclohexanedicarboxylic acid residue, 1,3-cyclopentanedicarboxylic acid residue, 1,3-cyclohexanedicarboxylic acid residue, 1,2- It contains at least one group selected from the group consisting of a cyclohexanedicarboxylic acid residue, a 1,2-cyclopropanedicarboxylic acid residue, and a 1,2-cyclobutanedicarboxylic acid residue.

The amount of the alicyclic polycarboxylic acid residue (a10) relative to the polyvalent carboxylic acid residue (a1) is preferably in the range of 30 to 99 mol%. When the amount of the alicyclic polyvalent carboxylic acid residue (a10) is 30 mol% or more, the primer layer 3 can have particularly high transparency. The amount of the alicyclic polyvalent carboxylic acid residue (a10) is more preferably 40 mol% or more.

The glycol residue (a2) is, for example, ethylene glycol residue, diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, pentaethylene glycol residue, hexaethylene glycol residue, heptaethylene glycol residue, octaethylene. Polyethylene glycol residues such as glycol residues; polypropylene glycol residues such as propylene glycol residues, dipropylene glycol residues, tripropylene glycol residues, tetrapropylene glycol residues; 1,3-propanediol residues, 1, 3-butanediol residue, 1,4-butanediol residue, 1,5-pentanediol residue, 1,6-hexanediol residue, 2,2-dimethyl-1,3-propanediol residue, 2 -Ethyl-2-butyl-1,3- Lopandiol residue, 2-ethyl-2-isobutyl-1,3-propanediol residue, 2,2,4-trimethyl-1,6-hexanediol residue, 1,2-cyclohexanedimethanol residue, 1, 3-cyclohexanedimethanol residue, 1,4-cyclohexanedimethanol residue, 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue, 4,4′-dihydroxybiphenol residue, 4, 4'-methylenediphenol residue, 4,4'-isopropylidenediphenol residue, 1,5-dihydroxynaphthalene residue, 2,5-dihydroxynaphthalene residue, 2,2-bis (4-hydroxyphenyl) It can contain at least one group selected from the group consisting of propane (bisphenol A) residues and bisphenol S residues.

In particular, the glycol residue (a2) is an ethylene glycol residue; a diethylene glycol residue; a butanediol residue such as a 1,4-butanediol residue; a hexanediol residue such as a 1,6-hexanediol residue; , 4-cyclohexanedimethanol residue; neopentyl glycol residue; and at least one group selected from the group consisting of bisphenol A residues. In this case, the synthesis of the saturated polyester resin (a) is easy, and the saturated polyester resin (a) can have high durability.

It is also preferred that the glycol residue (a2) contains an alicyclic glycol residue (a20). In this case, the primer layer 3 can have particularly high transparency.

The alicyclic glycol residue (a20) is selected from the group consisting of 1,4-cyclohexanedimethanol residue, 1,2-cyclobutanedimethanol residue, and 1,2-cyclopropanedimethanol residue, for example. Contains at least one group.

The amount of the alicyclic glycol residue (a20) relative to the glycol residue (a2) is preferably in the range of 30 to 100 mol%. When the amount of the alicyclic glycol residue (a20) is 30 mol% or more, the primer layer 3 can have particularly high transparency. The amount of the alicyclic glycol residue (a20) is more preferably 40 mol% or more.

The glycol residue (a2) preferably does not contain a trivalent or higher valent glycol residue. When the glycol residue (a2) contains a trivalent or higher valent glycol residue, the amount of the trivalent or higher valent glycol residue relative to the glycol residue (a2) is preferably 1 mol% or less. In these cases, since the presence of excessive crosslinking in the saturated polyester resin (a) is suppressed, the saturated polyester resin (a) may have higher water solubility or water dispersibility.

As described above, the saturated polyester resin (a) has an acid value within the range of 10 to 100 mgKOH / g. Therefore, the saturated polyester resin (a) functions effectively as an emulsifier, the saturated polyester resin (a) has a particularly high water solubility or water dispersibility, and the polymerization reaction product (A) is added to the primer layer 3. Particularly high adhesion can be imparted. The acid value of the saturated polyester resin (a) can be controlled, for example, by adjusting the amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1). In order for the saturated polyester resin (a) to function particularly effectively as an emulsifier, the acid value of the saturated polyester resin (a) is preferably 20 mgKOH / g or more, and more preferably 30 mgKOH / g or more. The acid value is preferably 95 mgKOH / g or less, and more preferably 90 mgKOH / g or less.

The weight average molecular weight of the saturated polyester resin (a) is preferably in the range of 3000 to 50000. When the weight average molecular weight is 3000 or more, the primer layer 3 can have particularly high adhesiveness. Further, when the weight average molecular weight is 50000 or less, the saturated polyester resin (a) may have particularly high water solubility or water dispersibility. The weight average molecular weight is more preferably 4000 or more, and even more preferably 5000 or more. The weight average molecular weight is more preferably 30000 or less, and even more preferably 20000 or less. The weight average molecular weight of the saturated polyester resin (a) can be easily adjusted by appropriately setting the synthesis conditions of the saturated polyester resin (a). In addition, the weight average molecular weight of saturated polyester resin (a) is a value (polystyrene conversion) measured by gel permeation chromatography.

The glass transition temperature of the saturated polyester resin (a) is preferably in the range of 0 to 80 ° C. It can suppress that the primer layer 3 has an excessively high tack property because this glass transition temperature is 0 degreeC or more. Further, when the glass transition temperature is 80 ° C. or lower, good moldability when forming the primer layer 3 from the primer composition can be obtained. The glass transition temperature is more preferably 10 ° C. or higher, and further preferably 15 ° C. or higher. The glass transition temperature is more preferably 70 ° C. or lower, and further preferably 65 ° C. or lower.

The saturated polyester resin (a) can be obtained, for example, by polymerizing a reactive raw material containing a compound having an ester-forming functional group. The ester-forming functional group means a functional group that can react with a carboxyl group or a hydroxyl group to form an ester bond. Examples of the ester-forming functional group include a carboxyl group, a hydroxyl group, an ester-forming derivative group of a carboxyl group, and an ester-forming derivative group of a hydroxyl group. The carboxyl group ester-formation-inducing group is a group that can be obtained by reacting a carboxyl group with some compound and can react with a hydroxyl group to form an ester bond. Specific examples of the ester forming derivative group of the carboxyl group are a group obtained by anhydride-forming the carboxyl group, a group obtained by esterifying the carboxyl group, obtained by acid chloride conversion of the carboxyl group, and halogenating the carboxyl group. Group obtained. The ester forming property-inducing group of a hydroxyl group is a group that can be obtained by reacting a hydroxyl group with some compound and can react with a carboxyl group to form an ester bond. Specific examples of the ester forming derivative group of the hydroxyl group include a group obtained by acetating the hydroxyl group. In particular, it is preferable that the ester-forming functional group is a carboxyl group or a hydroxyl group in that the reactivity during production of the saturated polyester resin (a) becomes good.

The reactive raw materials are a polyvalent carboxylic acid component corresponding to the polyvalent carboxylic acid residue (a1) in the saturated polyester resin (a) and a glycol corresponding to the glycol residue (a2) in the saturated polyester resin (a). Containing ingredients. The polyvalent carboxylic acid component contains at least one compound selected from the group consisting of polyvalent carboxylic acids and ester-forming derivatives of polyvalent carboxylic acids. The ester-forming derivative of a polyvalent carboxylic acid is a compound in which the carboxyl group in the polyvalent carboxylic acid is substituted with an ester-forming derivative group of the carboxyl group. The glycol component contains at least one compound selected from the group consisting of glycol and an ester-forming derivative of glycol. The ester-forming derivative of glycol is a compound in which a hydroxyl group in glycol is substituted with an ester-forming derivative group of a hydroxyl group.

The molar ratio of the polyvalent carboxylic acid component and the glycol component contained in the reactive raw material is preferably in the range of 1: 1 to 2.5.

The saturated polyester resin (a) is synthesized from a reactive raw material by a known polyester production method. For example, the saturated polyester resin (a) is synthesized by a direct esterification reaction in which a polyvalent carboxylic acid and glycol are reacted in a one-step reaction.

When the polyvalent carboxylic acid component contains an ester-forming derivative of a polyvalent carboxylic acid and the glycol component contains glycol, this is a transesterification reaction between the ester-forming derivative of the polyvalent carboxylic acid and the glycol. The saturated polyester resin (a) may be synthesized through a first-stage reaction and a second-stage reaction in which the reaction product of the first-stage reaction is polycondensed. In the first stage reaction, all the reactive raw materials may be contained in the reaction system from the beginning, and a part of the reactive raw materials may be added to the reaction system during the ester polycondensation reaction. In the first stage reaction, when all of the reactive raw materials are contained in the reaction system from the beginning, for example, the reaction system is 150 to 260 ° C. under an inert gas atmosphere such as nitrogen gas under normal pressure conditions. The transesterification proceeds by gradually raising the temperature until heated. The second stage reaction proceeds in a temperature range of 160 to 280 ° C. under a reduced pressure of, for example, 6.7 hPa (5 mmHg) or less.

In the first stage reaction and the second stage reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compounds, etc. may be added as a catalyst in the reaction system at an arbitrary time.

In addition, since the ethylenically unsaturated monomer (b) contains the nonionic ethylenically unsaturated monomer (b1), the polymerization reaction product (A) has particularly high water dispersibility and dispersion stability. Yes.

Nonionic ethylenically unsaturated monomer (b1) contains, for example, (meth) acrylic acid ester. More specifically, the nonionic ethylenically unsaturated monomer (b1) includes, for example, methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid. Ethyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, cyclohexyl (meth) acrylate, tertiary butyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic At least one component selected from the group consisting of isopropyl acid, propyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, stearyl (meth) acrylate, and octyl (meth) acrylate contains. Note that “(meth) acryl” means at least one of acrylic and methacrylic, for example, “(meth) acrylic acid ester” means at least one of acrylic acid ester and methacrylic acid ester. .

The nonionic ethylenically unsaturated monomer (b1) preferably contains a monomer (b0) having a hydroxyl group. In this case, since the primer layer 3 can have a hydroxyl group derived from the monomer (b0), the primer layer 3 can have higher adhesion to the highly polar substrate 2 and the outer layer 4.

Examples of the monomer (b0) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Contains at least one component selected from the group consisting of butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate To do.

The amount of the monomer (b0) relative to the ethylenically unsaturated monomer (b) is preferably in the range of 1 to 40 mol%. If the amount of this monomer (b0) is 1 mol% or more, the primer layer 3 has particularly high adhesion to the highly polar base material 2 and particularly high adhesion to the highly polar outer layer 4. sell. Further, when the amount of the monomer (b0) is 40 mol% or less, the polymerization reaction product (A) can have particularly high water dispersibility and dispersion stability. The amount of this monomer (b0) is more preferably 5 mol% or more, and even more preferably 10 mol% or more. Further, the amount of the monomer (b0) is more preferably 30 mol% or less, and further preferably 25 mol% or less.

The ethylenically unsaturated monomer (b) consists only of, for example, a nonionic ethylenically unsaturated monomer (b1).

The polymerization reaction product (A) is synthesized by emulsion polymerization of the ethylenically unsaturated monomer (b) using the saturated polyester resin (a) as an emulsifier as described above. More specifically, for example, first, an aqueous solution containing the saturated polyester resin (a) is prepared. The amount of the saturated polyester resin (a) with respect to the aqueous solution is, for example, in the range of 5 to 50% by mass. The aqueous solution is heated to a temperature within the range of 60 to 100 ° C., for example, and the polymerization initiator is put into the aqueous solution while stirring. Further, the ethylenically unsaturated monomer (b) is added to the aqueous solution while maintaining the aqueous solution at a temperature within the range of 60 to 100 ° C. and stirring. By maintaining this aqueous solution at a temperature within the range of 60 to 100 ° C. for 60 to 300 minutes, for example, with stirring, the emulsion polymerization proceeds. Thereby, the polymerization reaction product (A) can be synthesized, and as a result, an aqueous dispersion containing the polymerization reaction product (A) is obtained.

When the polymerization reaction product (A) is synthesized, a polymer having at least one of a carboxyl group and a hydroxyl group is added to the reaction system at any time as a component for improving the water dispersibility of the polymerization reaction product (A). It may be added. This polymer is, for example, a group consisting of acrylic acid polymer, methacrylic acid polymer, styrene-acrylic acid polymer, styrene-methacrylic acid polymer, styrene-maleic acid polymer, styrene-maleic anhydride polymer, and polyvinyl alcohol. It can contain at least one selected from

The mass ratio of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) is preferably in the range of 99: 1 to 10:90. In this case, the dispersibility of the polymerization reaction product (A) in the aqueous dispersion obtained by synthesizing the polymerization reaction product (A) can be particularly high, and the polymerization reaction product (A in the primer composition) ) Can also be particularly high in dispersibility. Furthermore, the primer layer 3 can have particularly high transparency. This mass ratio is more preferably in the range of 90:10 to 20:80, and even more preferably in the range of 80:20 to 30:70.

The maleic acid modified polyolefin resin (B) may include a maleic anhydride modified polyolefin resin. The maleic acid-modified polyolefin resin (B) can contain a resin obtained by modifying a polyolefin resin with at least one of maleic acid and maleic anhydride.

The polyolefin resin is a polymer of a monomer containing, for example, an alkene having 2 to 8 carbon atoms. The alkene having 2 to 8 carbon atoms can contain at least one compound selected from the group consisting of ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene, and 1-octene, for example. .

The maleic acid-modified polyolefin resin (B) is, for example, a copolymer of at least one of maleic acid and maleic anhydride and an alkene. In this copolymer, at least one of maleic acid and maleic anhydride and the alkene may be randomly copolymerized, block copolymerized, or graft copolymerized.

Specific examples of the maleic acid-modified polyolefin resin (B) include the product name Auroren manufactured by Nippon Paper Industries Co., Ltd., the product name APTOLOK manufactured by Mitsubishi Chemical Corporation, the product name GENPOLY manufactured by LOTTE CHEMICAL CORPORATION, and the product name manufactured by Toyobo Co., Ltd. Hard Ren, Sumitomo Chemtex Co., Ltd. trade name Sumifit, Nippon Paper Industries Co., Ltd. trade name Super Clone, Nippon Polypro Co., Ltd. trade name Wintech, Mitsui Chemicals Co., Ltd. trade name Toughmer XM, Sumitomo Chemical Co., Ltd. Includes the product name Tough Selenium manufactured by the company and the product name LMPO manufactured by Idemitsu Retail Sales.

The maleic acid-modified polyolefin resin (B) has a nonpolar polyolefin skeleton. Therefore, the primer layer 3 can have high adhesiveness with nonpolar materials such as polyolefin. Furthermore, since the maleic acid-modified polyolefin resin (B) is modified with at least one of maleic acid and maleic anhydride, it also has a polar part. Therefore, the maleic acid-modified polyolefin resin (B) can have high dispersibility in the primer composition.

The mass ratio of the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B) is preferably in the range of 80:20 to 20:80. In this case, the primer layer 3 can have particularly high adhesiveness with a nonpolar material such as polyolefin.

Water (C) is a solvent or dispersion medium in the primer composition.

The primer composition may contain a hydrophilic organic solvent together with water (C) as a solvent or a dispersion medium. Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol and 2-propanol; glycol ethers such as propylene glycol monomethyl ether, ethyl cellosolve and butyl cellosolve; and ketones such as cyclohexanone. When the primer composition contains a hydrophilic organic solvent, the amount of the hydrophilic organic solvent with respect to the total amount of water (C) and the hydrophilic organic solvent is in the range of 0.1 to 50% by mass. preferable.

The primer composition may contain a leveling agent. For example, when the primer composition contains a hydrophilic organic solvent such as alcohol or glycol ether, the hydrophilic organic solvent can function as a leveling agent.

The primer composition may contain a crosslinking agent. The crosslinking agent can contain, for example, at least one selected from the group consisting of an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an isocyanate crosslinking agent, and an epoxy crosslinking agent.

The primer composition may contain other resin water dispersion. The other resin water dispersion can contain at least one selected from the group consisting of, for example, a urethane resin water dispersion, an acrylic resin water dispersion, a polyester resin water dispersion, and an olefin resin water dispersion.

The primer composition may further contain appropriate additives such as an antifoaming agent, a film forming aid, a pigment, and a dye.

The method for producing a primer composition according to this embodiment is a method for producing a primer composition containing a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). Synthesizing the polymerization reaction product (A) by emulsion polymerization of the ethylenically unsaturated monomer (b) in the mixture containing the resin (a) and the ethylenically unsaturated monomer (b); And mixing the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B). The production method includes, for example, synthesis of a polymerization reaction product (A) by emulsion polymerization of a nonionic ethylenically unsaturated monomer (b) using a saturated polyester resin (a) as an emulsifier, and Mixing the aqueous dispersion containing the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B).

The method for synthesizing the polymerization reaction product (A) and the method for obtaining the aqueous dispersion containing the polymerization reaction product (A) are as described above. The water in the aqueous dispersion can be directly used as water (C) in the primer composition, but in order to adjust the amount of water (C) in the primer composition, water can be further added to the aqueous dispersion. Good.

The laminated member 1 according to this embodiment will be described. As shown in FIG. 1, the laminated member 1 includes a base material 2 and a primer layer 3 on the base material 2. The primer layer 3 contains a dried product of the primer composition. In the present embodiment, the laminated member 1 further includes an outer layer 4 made of metal or resin on the primer layer 3. That is, the base material 2, the primer layer 3, and the outer layer 4 are laminated in this order.

The base material 2 is, for example, a plate shape, a sheet shape, or a film shape. Even if the substrate 2 is made of a nonpolar material, the adhesion between the substrate 2 and the primer layer 3 is high.

The base material 2 is made of a resin such as a thermoplastic resin, or made of a metal such as a steel plate. The substrate 2 is particularly preferably a film made from a thermoplastic resin. Examples of thermoplastic resins are polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate and other polyester resins; polyglycolic acid, polylactic acid and other polyhydroxycarboxylic Acids; aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate); polyamide resins such as nylon 6, nylon 66 and nylon 46; polyolefins such as polypropylene, polyethylene and ethylene-vinyl acetate copolymer A resin; a polyimide resin; a polyarylate resin; and a mixture containing two or more of these resins. The substrate 2 is preferably made from a polyolefin resin, and particularly preferably made from a polypropylene resin.

For example, the primer layer 3 can be produced on the substrate 2 by applying the primer composition to the substrate 2 and then drying it.

A method for producing the primer layer 3 when the substrate 2 is a polyolefin resin film such as a polypropylene resin film will be described.

After drying the polyolefin resin, it is melt-extruded to produce an unstretched polyolefin resin sheet. A uniaxially stretched polyolefin resin film is produced by stretching this polyolefin resin sheet in one direction with a heating roll or the like. Furthermore, a biaxially stretched polyolefin resin film is produced by stretching the uniaxially stretched polyolefin resin film in a direction orthogonal to the above direction, followed by heat treatment to complete the orientation.

By applying a primer composition to an unstretched polyolefin resin sheet, a uniaxially stretched polyolefin resin film or a biaxially stretched polyolefin resin film at any stage in the process of producing a biaxially stretched polyolefin resin film, Primer layer 3 can be produced.

For example, the primer layer 3 can be produced by an off-line method. That is, the primer layer 3 can be prepared by preparing a biaxially stretched polyolefin resin film and then applying the primer composition to the biaxially stretched polyolefin resin film and drying it.

The primer layer 3 may be produced by an in-line method. That is, you may produce the primer layer 3 in the process of producing a biaxially stretched polyolefin resin film from polyolefin resin. In this case, for example, after preparing the primer layer 3 by applying the primer composition to an unstretched polyolefin resin sheet and drying it, the unstretched polyolefin resin sheet is sequentially stretched in two directions, and further subjected to heat treatment. By applying, a biaxially stretched polyolefin resin film can be produced. Moreover, after preparing the primer layer 3 by apply | coating a primer composition to a uniaxially stretched polyolefin resin film and making it dry, by extending | stretching a uniaxially stretched polyolefin resin film and also heat-processing, biaxially stretched polyolefin A resin film may be produced.

In this embodiment, since the primer composition particularly contains water (C) as a solvent or a dispersion medium, the organic solvent does not volatilize or the organic solvent volatilizes in the process of preparing the primer layer 3 from the primer composition. The amount is suppressed. For this reason, the danger that an organic solvent will ignite by the heat | fever at the time of extending | stretching and heat processing in the process of producing a biaxially stretched polyolefin resin film from polyolefin resin is low. Therefore, in both the off-line method and the in-line method, the primer layer 3 can be produced from the primer composition while suppressing the risk of ignition.

In addition, when the primer composition contains water (C) as a solvent or a dispersion medium, the organic solvent is difficult to be released from the primer composition to the environment, which is environmentally friendly.

An appropriate resin or metal outer layer 4 can be formed on the primer layer 3. The outer layer 4 is, for example, a photographic photosensitive layer; a diazo photosensitive layer; a matte layer; a magnetic layer; an inkjet ink receiving layer; a hard coat layer; a paint layer; a layer composed of an ultraviolet curable resin, a thermosetting resin, printing ink, UV ink, etc .; A layer of adhesive by lamination or extrusion lamination; vacuum deposition of metal, inorganic or oxide thereof; thin film layer formed by electron beam deposition, sputtering, ion plating, CVD or plasma polymerization; or organic barrier layer . The primer layer 3 may have high adhesiveness with various resin or metal outer layers 4.

(1) Preparation of Samples A to G Samples A to G, which are aqueous dispersions containing a saturated polyester resin, were prepared as follows.

A 1000 ml reaction vessel equipped with a stirrer, a nitrogen gas inlet, a thermometer, a rectifying column, and a cooling condenser was prepared. Components other than trimellitic anhydride in the column of “raw material component of saturated polyester resin” in Tables 1 and 2 in this reaction vessel were added to obtain a mixture. These were heated to 200 ° C. while stirring and mixing in a normal pressure and nitrogen atmosphere, and then gradually heated to 250 ° C. over 4 hours to complete the esterification reaction and the transesterification reaction. Next, trimellitic anhydride in the column of “raw material component of saturated polyester resin” in Tables 1 and 2 is added to this mixture, and the pressure is gradually reduced to 0.67 hPa (0.5 mmHg) at a temperature of 230 ° C. From this, the polycondensation reaction was advanced by maintaining for 2 hours in this state, and a saturated polyester resin was synthesized.

Saturated polyester resin, isopropyl alcohol, 25% aqueous ammonia and water were put in a container at a mass ratio shown in the column of “Sample composition” in Tables 1 and 2. By maintaining these at a temperature of 75 to 85 ° C. for 2 hours while stirring, an aqueous dispersion having a saturated polyester resin concentration of 25% by mass was obtained.

The weight average molecular weight, glass transition temperature, and acid value of the saturated polyester resin are as shown in Tables 1 and 2.

(2) Preparation of Samples A-1 to G-1 Samples A-1 to G-1 that are aqueous dispersions containing a polymerization reaction product were prepared as follows.

A reaction vessel having a capacity of 2000 ml equipped with a stirrer, a nitrogen gas inlet, a thermometer, a dropping funnel and a reflux condenser was prepared, and this reaction vessel is shown in the column of “Saturated polyester resin aqueous dispersion” in Tables 3 and 4. The ingredients were charged and heated to 80 ° C. with stirring under a nitrogen gas atmosphere. Next, after putting 2 parts by mass of an aqueous solution of ammonium persulfate having a concentration of 5% by mass as a polymerization initiator in the reaction vessel, the contents of the reaction vessel were stirred, and the “ethylenic unsaturation in Tables 3 and 4 were added. The components shown in the “Monomer” column were added dropwise over 2 hours. Next, after adding 2 parts by mass of an aqueous solution of ammonium persulfate having a concentration of 5% by mass in the reaction vessel, the emulsion polymerization product is maintained at a temperature of 80 ° C. for 3 hours while stirring the contents of the reaction vessel. Was synthesized.

Furthermore, when preparing Sample B-2, 50 parts by mass of an acrylic resin aqueous dispersion having a concentration of 20% by mass was added to the contents of the reaction vessel. The acrylic resin aqueous dispersion was stirred at a temperature of 75 to 85 ° C. for 2 hours while stirring 100 parts by weight of acrylic resin (BASF, product name Joncryl 680), 25 parts by weight of 25% ammonia water, and 375 parts by weight of water. It was prepared by holding.

Further, when preparing Sample C-3, 100 parts by mass of an aqueous dispersion of styrene maleic anhydride copolymer having a concentration of 20% by mass was added to the contents of the reaction vessel. When preparing Sample F-1, 50 parts by mass of an aqueous dispersion of styrene maleic anhydride copolymer having a concentration of 20% by mass was added to the contents of the reaction vessel. The aqueous dispersion of styrene maleic anhydride copolymer was prepared by stirring 100 parts by weight of styrene maleic anhydride copolymer (product name: SMA 1440, manufactured by Clay Valley), 25 parts by weight of 25% aqueous ammonia, and 375 parts by weight of water. It was prepared by holding at a temperature of ˜85 ° C. for 2 hours.

Thereby, an aqueous dispersion containing a polymerization reaction product was obtained.

In the column of “mass ratio of saturated polyester resin and ethylenically unsaturated monomer” in Tables 3 and 4, the mass ratio of saturated polyester resin and ethylenically unsaturated monomer in the aqueous dispersion of saturated polyester resin Indicates.

(3) Preparation of Sample A-mix Sample A-mix was prepared as follows.

Prepare a reaction vessel with a capacity of 1000 ml equipped with a stirrer, nitrogen gas inlet, thermometer, dropping funnel, reflux condenser, and put 240 parts by mass of ion-exchanged water and 5 parts by mass of sodium lauryl sulfate into this reaction vessel. The mixture was heated to 80 ° C. with stirring under a nitrogen gas atmosphere. Next, 2 parts by mass of an aqueous solution of ammonium persulfate having a concentration of 5% by mass as a polymerization initiator is placed in the reaction container, and then 60 parts by mass of methyl methacrylate and butyl methacrylate 40 are placed in the reaction container while stirring the contents of the reaction container. Part by mass was added dropwise over 2 hours. Next, after adding 2 parts by mass of an aqueous solution of ammonium persulfate having a concentration of 5% by mass in the reaction vessel, the emulsion polymerization product is maintained at a temperature of 80 ° C. for 3 hours while stirring the contents of the reaction vessel. An aqueous dispersion was prepared.

The mass ratio of the aqueous dispersion of this emulsion polymer and Sample A to the total amount of methyl methacrylate and butyl methacrylate used in the synthesis of the saturated polyester resin in Sample A and the emulsion polymer was 1: 1. The sample A-mix was obtained by mixing.

(4) Preparation of Sample C-mix Sample C-mix was prepared as follows.

Prepare a reaction vessel with a capacity of 1000 ml equipped with a stirrer, nitrogen gas inlet, thermometer, dropping funnel, reflux condenser, and put 240 parts by mass of ion-exchanged water and 5 parts by mass of sodium lauryl sulfate into this reaction vessel. The mixture was heated to 80 ° C. with stirring under a nitrogen gas atmosphere. Next, after putting 2 parts by mass of an aqueous solution of ammonium persulfate having a concentration of 5% by mass as a polymerization initiator in the reaction vessel, 40 parts by mass of methyl methacrylate and 40% of butyl methacrylate are put into the reaction vessel while stirring the contents of the reaction vessel. Part by mass and 20 parts by mass of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. Next, after adding 2 parts by mass of an aqueous solution of ammonium persulfate having a concentration of 5% by mass in the reaction vessel, the emulsion polymerization product is maintained at a temperature of 80 ° C. for 3 hours while stirring the contents of the reaction vessel. An aqueous dispersion was prepared.

The aqueous dispersion of this emulsion polymer and sample C were combined with the saturated polyester resin in sample C and the total amount of methyl methacrylate, butyl methacrylate and 2-hydroxyethyl methacrylate used for the synthesis of the emulsion polymer. Sample C-mix was obtained by mixing so that the mass ratio was 3: 2.

(5) Preparation of Examples 1 to 19 and Comparative Examples 1 to 4 Primer compositions 1 to 19 and Comparative Examples 1 to 4 were prepared as follows.

In Tables 5 and 6, the components shown in the column “Aqueous dispersion containing polymerization reaction product” and the components shown in the column “Modified polyolefin resin solution” were mixed to prepare Examples 11, 17 and 19. Sometimes the components shown in “Additives” were also mixed to obtain a mixed solution. A primer composition having a solid content concentration of 25% by mass was obtained by adding a butyl cellosolve aqueous solution having a concentration of 30% by mass as a leveling agent to the mixed solution.

The components shown in the column of “Modified polyolefin resin solution” in Tables 5 and 6 are aqueous dispersions of maleic acid-modified polyolefin resin, the details of which are as follows.
-GENPOLY HGW9566: LOTTE CHEMICAL CORPORATION product name GENPOLY HGW9566. An aqueous dispersion of a maleic anhydride-modified polypropylene resin. Weight average molecular weight 40000 or more.
Auroren AE-301: Nippon Paper Industries Co., Ltd., trade name Auroren AE-301. An aqueous dispersion of maleic anhydride / acrylic modified polyolefin resin. Weight average molecular weight 80,000 to 100,000.
Auroren AE-501: Nippon Paper Industries Co., Ltd., trade name Auroren AE-501. Aqueous dispersion of maleic anhydride-modified polyolefin resin, weight average molecular weight of 100,000 to 1500,000.
APTOLOK BW-5550: Mitsubishi Chemical Corporation, trade name APTOLOK BW-5550. An aqueous dispersion of a copolymer of maleic anhydride-modified polypropylene and methoxypoly (oxyethylene / oxypropylene) -2-propylamine. Weight average molecular weight 135000.

Details of the components shown in the column “Additives” in Tables 5 and 6 are as follows.
Epocross WS-700: Oxazoline group-containing water-soluble polymer, manufactured by Nippon Shokubai Co., Ltd., product name Epocross WS-700.
Carbodilite SV-02: An aqueous cross-linking agent obtained by adding a hydrophilic segment to a polycarbodiimide resin, manufactured by Nisshinbo Chemical Co., Ltd., product name Carbodilite SV-02.

(6) Physical property test The following tests were conducted on the primer compositions of Examples 1 to 19 and Comparative Examples 1 to 4.

(6-1) Preparation of primer layer An untreated polypropylene film was prepared as a substrate. On this base material, the primer composition was applied with a bar coater and then heated at 120 ° C. for 5 minutes. Thereby, a primer layer having a thickness of 1 μm was formed on the substrate.

(6-2) Haze Only in the case of this haze test, a primer layer having a thickness of 3 μm was formed using a polyethylene terephthalate film (product name: Lumirror T60 # 100, manufactured by Toray Industries, Inc.) as a base material. Subsequently, the haze of only the base material and the haze obtained by combining the base material and the primer layer were measured using a haze meter NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd. A value obtained by subtracting the haze of only the base material from the haze of the base material and the primer layer was calculated as the haze of the primer layer.

(6-3) Room temperature tackiness An untreated polypropylene film was prepared as a member to be superimposed on the primer layer on the substrate. In a state where this member was stacked on the primer layer, the member and the primer layer were bonded together under the conditions of a temperature of 25 ° C., a humidity of 60%, a pressure of 0.1 MPa, and a pressure bonding time of 1 hour. Then, the tack property under normal temperature between the primer layer and the member was confirmed. As a result, “A” indicates that no tack is observed at the interface between the primer layer and the member, “B” indicates that tack is recognized in a part of the interface, and “B” indicates that tack is recognized in most part of the interface. C ".

(6-4) Adhesiveness to base material A cellophane adhesive tape was adhered to the primer layer on the base material and peeled off, and the state of the remaining primer layer was observed. As a result, “A” indicates that no peeling of the primer layer is observed, “B” indicates that peeling is observed in a small part of the primer layer, “C” indicates that peeling is recognized in a part of the primer layer, The case where peeling was observed in most of the primer layer was evaluated as “D”.

(6-5) Adhesiveness of paint layer On the primer layer on the substrate, an acrylic resin-based aqueous white paint was applied with a bar coater and then heated at 120 ° C for 5 minutes. Thereby, a paint layer having a thickness of 2 μm was formed on the primer layer. The cellophane adhesive tape was adhered to the paint layer and then peeled off, and the state of the remaining paint layer was observed. As a result, “A” indicates that peeling of the paint layer is not observed, “B” indicates that peeling is observed in a small part of the paint layer, “C” indicates that peeling is recognized in part of the paint layer, The case where peeling was observed in the most part of the paint layer was evaluated as “D”.

(6-6) Adhesiveness of aluminum vapor deposition layer An aluminum vapor deposition layer having a thickness of about 1 μm was formed on the primer layer on the substrate by a vacuum vapor deposition process. The cellophane adhesive tape was adhered to the aluminum vapor deposition layer and then peeled off, and the state of the remaining aluminum vapor deposition layer was observed. As a result, “A” indicates that peeling of the aluminum deposited layer is not recognized, “B” indicates that peeling is observed in a small portion of the aluminum deposited layer, and “B” indicates that peeling is observed in some of the aluminum deposited layer. "C" and the case where peeling was recognized in the most part of the aluminum vapor deposition layer were evaluated as "D".

As apparent from the above-described embodiment, the primer composition according to the first aspect contains a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The polymerization reaction product (A) is produced by emulsion polymerization of the ethylenically unsaturated monomer (b) in the mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b). Product. The saturated polyester resin (a) has an acid value within the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

In the primer composition according to the second aspect, in the first aspect, the mass ratio of the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B) is in the range of 80:20 to 20:80. It is.

In the primer composition according to the third aspect, in the first or second aspect, the saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2). The carboxylic acid residue (a1) contains a trivalent or higher polyvalent carboxylic acid residue (a11), and the amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is: It is in the range of 1 to 50 mol%.

In the primer composition according to the fourth aspect, in the third aspect, the polyvalent carboxylic acid residue (a1) contains an alicyclic polyvalent carboxylic acid residue (a10), and the polyvalent carboxylic acid residue The amount of the alicyclic polyvalent carboxylic acid residue (a10) relative to (a1) is in the range of 30 to 99 mol%.

In the primer composition according to the fifth aspect, in the third or fourth aspect, the glycol residue (a2) contains an alicyclic glycol residue (a20), and is a fatty acid for the glycol residue (a2). The amount of the cyclic glycol residue (a20) is in the range of 30 to 100 mol%.

In the primer composition according to the sixth aspect, in the first to fifth aspects, the mass ratio of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) is 99: 1 to 10:90. Is within the range.

In the primer composition according to the seventh aspect, in the first to sixth aspects, the nonionic ethylenically unsaturated monomer (b1) contains a monomer (b0) having a hydroxyl group, The amount of the monomer (b0) having a hydroxyl group with respect to the saturated monomer (b) is in the range of 1 to 40 mol%.

The laminated member according to the eighth aspect includes a base material and a primer layer on the base material, and the primer layer contains a dried product of the primer composition according to the first to seventh aspects.

In the eighth aspect, the laminated member according to the ninth aspect includes a metal or resin outer layer on the primer layer.

The method for producing a primer composition according to the tenth aspect is a method for producing a primer composition containing a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). This production method comprises a polymerization reaction product (emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b) ( Synthesizing A) and mixing the polymerization reaction product (A) with the maleic acid-modified polyolefin resin (B). The saturated polyester resin (a) has an acid value within the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

The method for producing a primer composition according to the eleventh aspect is the tenth aspect, wherein the saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2). The carboxylic acid residue (a1) contains a trivalent or higher polyvalent carboxylic acid residue (a11), and the amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is Within the range of 1 to 50 mol%.

Claims

Containing a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C);
The polymerization reaction product (A) emulsion-polymerizes the ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b). Is a product produced by
The saturated polyester resin (a) has an acid value within a range of 10 to 100 mgKOH / g,
The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).
Primer composition.
The mass ratio of the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B) is in the range of 80:20 to 20:80.
The primer composition according to claim 1.
The saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2),
The polyvalent carboxylic acid residue (a1) contains a trivalent or higher polyvalent carboxylic acid residue (a11),
The amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is in the range of 1 to 50 mol%.
The primer composition according to claim 1 or 2.
The polyvalent carboxylic acid residue (a1) contains an alicyclic polyvalent carboxylic acid residue (a10),
The amount of the alicyclic polycarboxylic acid residue (a10) relative to the polycarboxylic acid residue (a1) is in the range of 30 to 99 mol%.
The primer composition according to claim 3.
The glycol residue (a2) contains an alicyclic glycol residue (a20),
The amount of the alicyclic glycol residue (a20) relative to the glycol residue (a2) is in the range of 30 to 100 mol%.
The primer composition according to claim 3 or 4.
The mass ratio of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) is in the range of 99: 1 to 10:90.
The primer composition according to any one of claims 1 to 5.
The nonionic ethylenically unsaturated monomer (b1) contains a monomer (b0) having a hydroxyl group,
The amount of the monomer (b0) having a hydroxyl group with respect to the ethylenically unsaturated monomer (b) is in the range of 1 to 40 mol%.
The primer composition according to any one of claims 1 to 6.
A substrate and a primer layer on the substrate;
The primer layer contains a dried product of the primer composition according to any one of claims 1 to 7.
Laminated member.
Comprising a metal or resin outer layer on the primer layer;
The laminated member according to claim 8.
A method for producing a primer composition comprising a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C),
The polymerization reaction product (A) is obtained by emulsion polymerization of the ethylenically unsaturated monomer (b) in the mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b). Synthesizing and mixing the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B),
The saturated polyester resin (a) has an acid value within a range of 10 to 100 mgKOH / g,
The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).
A method for producing a primer composition.
The saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2),
The polyvalent carboxylic acid residue (a1) contains a trivalent or higher polyvalent carboxylic acid residue (a11),
The amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is in the range of 1 to 50 mol%.
The manufacturing method of the primer composition of Claim 10.