TWI660012B - Primer composition, laminated member and manufacturing method of primer composition - Google Patents

Abstract

The present invention provides a primer composition capable of forming a primer layer having high adhesion and transparency by coating on a substrate.

The primer composition 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) is a product produced by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an 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) contains a nonionic ethylenically unsaturated monomer (b1).

Description

Primer composition, laminated member and manufacturing method of primer composition

The present invention relates to a primer composition, a laminated member, and a method for manufacturing the primer composition. In particular, it relates to a primer composition used to form a primer layer and a laminated member provided with the primer. A primer layer formed by a paint composition; and a method for manufacturing the primer composition.

On various substrates, for example, films made of polyolefin resins such as polypropylene and polyethylene, coating may be performed, ink may be provided for printing, or a metal vapor-deposited layer may be provided to provide 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, the substrate may be subjected to corona discharge, plasma treatment, flame treatment, ultraviolet irradiation treatment, Surface treatment such as solvent treatment.

However, these surface treatments involve problems involving dangerous operations. In addition, there is a problem that the adhesiveness improved by surface treatment is liable to decrease with the passage of time.

Therefore, in order to improve the adhesiveness of the substrate, a treatment of applying a primer having excellent adhesiveness to the substrate was previously performed.

As such a primer, for example, Patent Document 1 discloses a primer including a main agent (A) composed of a copolymer composed of an unsaturated compound having a hydroxyl group and an unsaturated compound. One or more unsaturated compounds in the group consisting of carboxylic acid esters, styrene, unsaturated carboxylic acids, unsaturated hydrocarbons, vinyl esters, and vinyl halides are used as monomers; the hardener (B) consists of isocyanate groups And a compound (C) having two or more carboxylic acid groups or one or more carboxylic acid anhydride groups in one molecule.

For primers, not only high adhesion but also high transparency are sometimes required. For example, when only a part of the surface of the substrate is coated, or when the substrate is coated with high transparency, the primer layer formed of the primer may be required to have high transparency.

[Prior technical literature]

(Patent Literature)

Patent Document 1: International Publication No. WO2010 / 038643

An object of the present invention is to provide a primer composition, a laminated member, and a method for manufacturing the primer composition. The primer composition can form a primer with high adhesion and transparency by coating on a substrate. Layer, the laminated member includes a primer layer formed of the primer composition.

A primer composition according to one aspect of the present invention includes a polymerization reaction product (A), a maleic acid modified polyolefin resin (B), and water (C). The polymerization reaction product (A) is obtained by reducing the ethylenic saturation in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b). Product produced by emulsion polymerization with monomer (b). The saturated polyester resin (a) has an acid value in a range of 10 to 100 mgKOH / g. The said ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

A method for producing a primer composition according to an aspect of the present invention, the primer composition comprising a polymerization reaction product (A), a maleic acid modified polyolefin resin (B), and water (C). The method for producing the primer composition includes the steps of emulsifying and polymerizing the ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b), and This synthesizes the aforementioned polymerization reaction product (A); and mixes the aforementioned polymerization reaction product (A) with the aforementioned maleic acid modified polyolefin resin (B). The saturated polyester resin (a) has an acid value in a range of 10 to 100 mgKOH / g. The said ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

According to one aspect of the present invention, a primer composition, a laminated member, and a method for manufacturing the primer composition can be obtained. The primer composition can be formed on the substrate to form adhesion and transparency. A high primer layer including a primer layer formed from the primer composition.

1‧‧‧Laminated components

2‧‧‧ substrate

3‧‧‧ primer layer

4‧‧‧ Outer

FIG. 1 is a cross-sectional view showing a laminated member according to an embodiment of the present invention.

The primer composition of this embodiment is used to obtain the laminated member 1 as shown in, for example, FIG. 1. The laminated member 1 includes a base material 2, a primer layer 3, and an outer layer 4, wherein the primer layer 3 is located on the base material 2 and contains a dried composition of the primer composition, and the outer layer 4 is located on the primer layer 3 and It is made of metal or resin.

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 a product produced by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an 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) contains a nonionic ethylenically unsaturated monomer (b1).

The primer composition 3 is coated on the base material 2 and then dried to form a primer layer 3 on the base material 2. The primer layer 3 can have high adhesion to the substrate 2 even if the substrate 2 is a film made of a polyolefin resin such as polypropylene or polyethylene. The adhesion between the primer layer 3 and the base material 2 is particularly achieved by the maleic acid modified polyolefin resin (B). When the outer layer 4 made of resin or metal is formed on the primer layer 3, the primer layer 3 can have high adhesion to the outer layer 4. The high adhesion between the primer layer 3 and the outer layer 4 is achieved in particular by the polymerization reaction product (A).

Furthermore, as described above, an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b) is subjected to emulsion polymerization to generate a polymerization reaction. Product (A), the primer layer 3 can have high transparency.

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

However, this embodiment is characterized in that not only the saturated polyester resin (a) and the emulsified polymer of the ethylenically unsaturated monomer (b) are mixed, but a polymerization reaction product (A) is produced by the method described above. When the ethylenically unsaturated monomer (b) is subjected to emulsion polymerization, the saturated polyester resin (a) can function as an emulsifier. Therefore, in this embodiment, the polymerization reaction product (A) can help improve the transparency of the primer layer 3 and also help improve the adhesion between the primer layer 3 and the outer layer 4.

Furthermore, since an emulsifier other than the saturated polyester resin (a) is not required during the emulsion polymerization, the primer composition may not contain 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), it is possible to suppress deterioration of the appearance and performance of the primer layer 3 caused by the bleeding of the emulsifier from the primer layer 3.

Furthermore, a polymer is synthesized by emulsifying and polymerizing the ethylenically unsaturated monomer (b) using an emulsifier other than the saturated polyester resin (a), and then the polymer is mixed with the saturated polyester resin (a) and cis. When the butadiene-modified polyolefin resin (B) and water (C) are mixed to prepare a composition, the transparency of the layer formed from the composition is lower than that of the primer layer 3 of this embodiment. Further, the adhesion between the layer formed by the composition and the outer layer 4 is worse than that of the primer layer 3 of this embodiment. That is, the aforementioned composition and layer are different from the primer composition and the primer layer 3 of this embodiment. However, even if the present inventors analyzed both by infrared absorption method and high-speed liquid chromatography, the analysis results between the two were also No significant difference could be identified. Therefore, the structure or characteristics of the polymerization reaction product (A) cannot be specifically specified in a literal manner.

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

The saturated polyester resin (a) has a polycarboxylic acid residue (a1) and a diol residue (a2).

The polycarboxylic acid residue (a1) contains, for example, at least one group selected from the group consisting of a ternary or higher polycarboxylic acid residue (a11), and a polycarboxylic acid residue having a metal sulfonic acid group. Group (a12), and a dicarboxylic acid residue (a13) other than these.

A polyvalent carboxylic acid residue (a11) of three or more members contains at least one group selected from the group consisting of 1,2,3-benzenetricarboxylic acid residue, 1,2,4-benzene Tricarboxylic acid residue, 1,3,5-benzenetricarboxylic acid residue, 1,2,3,5-benzenetetracarboxylic acid residue, 1,2,4,5-benzenetetracarboxylic acid residue, pyropentacarboxylic acid residue , Melic acid residues, cyclopropane-1,2,3-tricarboxylic acid residues, cyclopentane-1,2,3,4-tetracarboxylic acid residues, and ethanetetracarboxylic acid residues.

The polycarboxylic acid residue (a12) having a metal sulfonic acid group is, for example, a dicarboxylic acid residue having a metal sulfonic acid group. More specifically, the polycarboxylic acid residue (a12) contains, for example, at least one group selected from the group consisting of 5-sulfoisophthalic acid residue, 2-sulfoisophthalic acid Residues, 4-sulfoisophthalic acid residues, 2-sulfoterephthalic acid residues, and 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 residue containing, for example, at least one selected from the group consisting of Group: terephthalic acid residue, isophthalic acid residue, phthalic acid residue, biphthalic acid residue, naphthalenedicarboxylic acid residue, 1,2-naphthalenedicarboxylic acid residue, 1,4- Naphthalenedicarboxylic acid residues, 1,5-naphthalenedicarboxylic acid residues, and 2,6-naphthalenedicarboxylic acid residues. Aliphatic dicarboxylic acid residues containing, for example, at least one group selected from the group consisting of linear, branched, and alicyclic oxalic acid residues, malonic acid residues, and succinic acid residues , Maleic acid residue, itaconic acid residue, glutaric acid residue, adipic acid residue, pimelic acid residue, 2,2-dimethylglutaric acid residue, suberic acid residue Group, 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, oxydiacetic acid residue, and Thiopropionic acid residues. Terephthalic acid residues, isophthalic acid residues and 2,6-naphthalenedicarboxylic acid residues in aromatic dicarboxylic acid residues, succinic acid residues and adipic acid residues in aliphatic dicarboxylic acid residues Acid residue, sebacic acid residue, dodecanedioic acid residue, and 1,4-cyclohexanedicarboxylic acid residue, from the ease of reaction, the adhesiveness of the obtained resin, weather resistance, durability It ’s more appropriate in other aspects. Particularly preferably, the aromatic dicarboxylic acid residue and the 1,4-cyclohexanedicarboxylic acid residue are the main components of the polycarboxylic acid residue (a1).

The polycarboxylic acid residue (a1) preferably contains a polyvalent carboxylic acid residue (a11) having three or more members. In this case, the saturated polyester resin (a) can have a carboxyl group derived from a polyvalent carboxylic acid residue (a11) having a ternary or higher value. 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. further, The saturated polyester resin (a) can provide the primer layer 3 with high adhesion to the base material 2 and the outer layer 4.

The amount of the polycarboxylic acid residue (a11) relative to the polycarboxylic acid residue (a1) is preferably in the range of 1 to 50 mole%. With the amount of the polycarboxylic acid residue (a11) in the range of 1 to 50 mole%, the saturated polyester resin (a) functions particularly effectively as an emulsifier, and the saturated polyester resin (a) has a special High water solubility or water dispersibility, and further, the saturated polyester resin (a) can provide particularly high adhesion to the primer layer 3. The amount of the polycarboxylic acid residue (a11) is more preferably 5 mol% or more, and still more preferably 10 mol% or more. The amount of the polycarboxylic acid residue (a11) is more preferably 45 mol% or less, and still more preferably 40 mol% or less.

The polycarboxylic acid residue (a1) may contain a polycarboxylic acid residue (a12) having a metal sulfonic acid group. At this time, the saturated polyester resin (a) can have a metal sulfonic acid group derived from a polycarboxylic acid residue (a12), and the metal sulfonic acid group is a polar group. Therefore, the saturated polyester resin (a) has particularly high water solubility or water dispersibility, and further, the polymerization reaction product (A) can impart particularly high adhesion to the primer layer 3.

Among them, in order to impart high water resistance to the primer layer 3, the amount of the polycarboxylic acid residue (a1) relative to the polycarboxylic acid residue (a1) is preferably 3 mole% or less, and more preferably 1 mole %the following.

The polycarboxylic acid residue (a1) also preferably contains an alicyclic polycarboxylic acid residue (a10). In this case, the primer layer 3 can have particularly high transparency.

An alicyclic polycarboxylic acid residue (a10) containing, for example, at least one group selected from the group consisting of 1,4-cyclohexanedicarboxylic acid residue, 1,3-cyclopentanedi Formic acid residue, 1,3-cyclohexanedicarboxylic acid residue, 1,2-cyclohexanedicarboxylic acid residue, 1,2-cyclopropanedicarboxylic acid residue, and 1,2-cyclobutanedicarboxylic acid residue base.

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

The diol residue (a2) may contain, for example, at least one group selected from the group consisting of a glycol residue, a diethylene glycol residue, a triethylene glycol residue, and tetraethylene glycol. Polyethylene glycol residues such as alcohol residues, pentaethylene glycol residues, hexaethylene glycol residues, heptaethylene glycol residues, and octaethylene glycol residues; propylene glycol residues, dipropylene glycol residues, and tripropylene glycol Polypropylene glycol residues such as residues, tetrapropylene glycol residues; 1,3-propanediol residues, 1,3-butanediol residues, 1,4-butanediol residues, 1,5-pentanediol residues , 1,6-hexanediol residue, 2,2-dimethyl-1,3-propanediol residue, 2-ethyl-2-butyl-1,3-propanediol 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'-dihydroxyl Biphenyl residues, 4,4'-methylene diphenol residues, 4,4'-isopropylidene di Phenol residue, 1,5-dihydroxynaphthalene residue, 2,5-dihydroxynaphthalene residue, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) residue, and bisphenol S residue base.

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

The diol residue (a2) also preferably contains an alicyclic diol residue (a20). In this case, the primer layer 3 can have particularly high transparency.

The alicyclic diol residue (a20) contains, for example, at least one group selected from the group consisting of 1,4-cyclohexanedimethanol residue, 1,2-cyclobutanedimethanol Residues, and 1,2-cyclopropanedimethanol residues.

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

It is preferable that the diol residue (a2) does not contain a diol residue of 3 or more members. When the diol residue (a2) contains a diol residue of 3 or more, it is preferable that the amount of the diol residue of 3 or more is 1 mol% or less with respect to the diol residue (a2). In such cases, excessive crosslinking in the saturated polyester resin (a) can be suppressed, so the saturated polyester resin (a) can have higher water solubility or water dispersibility.

As described above, the saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g. Therefore, the saturated polyester resin (a) effectively functions as an emulsifier, and the saturated polyester resin (a) has particularly high water solubility or water dispersibility, and further, the polymerization reaction product (A) can be used for the primer Layer 3 imparts particularly high adhesion. The acid value of the saturated polyester resin (a) can be controlled by, for example, adjusting the amount of the polycarboxylic acid residue (a11) with respect to the polycarboxylic 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, 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 3,000 to 50,000. When the weight average molecular weight is 3,000 or more, the primer layer 3 can have particularly high adhesion. When the weight average molecular weight is 50,000 or less, the saturated polyester resin (a) can have particularly high water solubility or water dispersibility. The weight average molecular weight is more preferably 4,000 or more, and still more preferably 5,000 or more. The weight average molecular weight is more preferably 30,000 or less, and still more preferably 20,000 or less. The weight average molecular weight of the saturated polyester resin (a) can be easily adjusted by appropriately setting the synthetic conditions of the saturated polyester resin (a). The weight average molecular weight of the saturated polyester resin (a) is a value (in terms of polystyrene) 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. Since the glass transition temperature is above 0 ° C, It is enough to suppress the primer layer 3 from having too high viscosity. Moreover, when this glass transition temperature is 80 degrees C or less, the favorable moldability at the time of forming the primer layer 3 from a primer composition can be obtained. The glass transition temperature is more preferably 10 ° C or higher, and still more preferably 15 ° C or higher. The glass transition temperature is more preferably 70 ° C or lower, and even more 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 refers to a functional group capable of reacting 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 hydroxy group. The ester-forming derivative of a carboxyl group is a group obtained by reacting a carboxyl group with some compounds and capable of reacting with a hydroxyl group to form an ester bond. Specific examples of the ester-forming derivative group of a carboxyl group include a group obtained by acidifying a carboxyl group; a group obtained by esterifying a carboxyl group; a group obtained by chlorinating a carboxyl group; and a group obtained by halogenating a carboxyl group. The so-called hydroxy-ester-forming derivative is a group obtained by reacting a hydroxy group with some compounds and reacting with a carboxyl group to form an ester bond. Specific examples of the hydroxy-ester-forming derivative group include a group obtained by esterifying glycolic acid. In particular, when the ester-forming functional group is a carboxyl group or a hydroxyl group, the reactivity at the time of producing the saturated polyester resin (a) becomes good, and this is preferable.

The reactive raw material contains a polycarboxylic acid component corresponding to the polycarboxylic acid residue (a1) in the saturated polyester resin (a) and a diol corresponding to the diol residue (a2) in the saturated polyester resin (a). ingredient. A polycarboxylic acid component containing a polycarboxylic acid and an ester-forming derivative thereof At least one compound in the group. The ester-forming derivative of a polycarboxylic acid is a compound formed by substituting a carboxyl group in a polycarboxylic acid with an ester-forming derivative of a carboxyl group. The diol component contains at least one compound selected from the group consisting of a diol and an ester-forming derivative of a diol. An ester-forming derivative of a diol is a compound obtained by substituting a hydroxyl group in a diol with an ester-forming derivative group of a hydroxyl group.

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

The saturated polyester resin (a) can be synthesized from a reactive raw material by a known polyester production method. For example, the saturated polyester resin (a) can be synthesized by a direct esterification reaction in which a polycarboxylic acid and a diol are reacted in a single-stage reaction.

When the polycarboxylic acid component contains an ester-forming derivative of a polycarboxylic acid and the diol component contains a diol, a saturated polyester resin (a) can also be synthesized through the following reaction: the first-stage reaction is a polycarboxylic acid The transesterification reaction of the ester-forming derivative with the diol; and the second-stage reaction, which is a polycondensation of the reaction product obtained from the first-stage reaction. In the first stage of the reaction, all of the reactive raw materials may be included in the reaction system from the beginning, or 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 reactive raw materials are included in the reaction system from the beginning, for example, the reaction system is gradually heated from 150 ° C to 260 ° C under an inert gas atmosphere such as nitrogen under normal pressure conditions. This undergoes a transesterification reaction. The second reaction, such as in It is carried out under a reduced pressure of 6.7 hPa (5 mmHg) or less within a temperature range of 160 to 280 ° C.

In the first stage reaction and the second stage reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compounds and the like can be added to the reaction system at any time as catalysts.

Moreover, since the ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1), the polymerization reaction product (A) can have particularly high water dispersibility and dispersion stability.

The nonionic ethylenically unsaturated monomer (b1) contains, for example, a (meth) acrylate. More specifically, the nonionic ethylenically unsaturated monomer (b1) contains, for example, at least one component selected from the group consisting of methyl (meth) acrylate and butyl (meth) acrylate Ester, 2-hydroxyethyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, (meth) acrylic acid Cyclohexyl ester, tertiary butyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, Hexyl (meth) acrylate, stearyl (meth) acrylate, and octyl (meth) acrylate. The "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid, and for example, the "(meth) acrylate" means at least one of acrylate and methacrylate.

The nonionic ethylenically unsaturated monomer (b1) preferably contains a monomer (b0) having a hydroxyl group. At this time, since the primer layer 3 can have a hydroxyl group derived from the monomer (b0), the primer layer 3 can have higher adhesion with the highly polar base material 2 and the outer layer 4.

The monomer (b0) having a hydroxyl group contains, for example, at least one component selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (methyl ) Acrylate, polypropylene glycol (meth) acrylate.

The amount of the monomer (b0) is preferably in the range of 1 to 40 mole% relative to the ethylenically unsaturated monomer (b). When the amount of the monomer (b0) is 1 mol% or more, the primer layer 3 can have particularly high adhesion with the highly polar base material 2 and has particularly high adhesion with the highly polar outer layer 4. 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 the monomer (b0) is more preferably 5 mol% or more, and still more preferably 10 mol% or more. The amount of the monomer (b0) is more preferably 30 mol% or less, and still more preferably 25 mol% or less.

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

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

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

The mass ratio of the saturated polyester resin (a) to the ethylenically unsaturated monomer (b) is preferably in the range of 99: 1 to 10:90. At this time, the dispersibility of the polymerization reaction product (A) in the water dispersion liquid obtained by synthesizing the polymerization reaction product (A) can become particularly high, and the polymerization reaction product (A) in the primer composition is dispersed. Sex can also become particularly high. Further, the primer layer 3 can have particularly high transparency. The quality 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 anhydride-modified polyolefin resin (B) can contain a maleic anhydride-modified polyolefin resin. Maleic acid modified polyolefin tree The lipid (B) may contain a resin obtained by modifying a polyolefin resin with at least one of maleic acid and maleic anhydride.

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

The maleic acid modified polyolefin resin (B) is, for example, a copolymer of at least one of maleic acid and maleic anhydride and an olefin. In this copolymer, at least one of maleic acid and maleic anhydride and olefins may be subjected to random copolymerization, block copolymerization, or graft copolymerization.

Specific examples of the maleic acid modified polyolefin resin (B) include: the trade name AUROREN manufactured by Nippon Paper Co., Ltd., the trade name APTOLOK manufactured by Mitsubishi Chemical Co., Ltd., the trade name GENPOLY manufactured by Lotte Chemical Corporation, Trade names HARDLEN manufactured by Toyobo Co., Ltd., SUMIFITT manufactured by SUMIKA CHEMTEX Co., Ltd., SUPERCHLON manufactured by Japan Paper Co., Ltd., trade name WINTEC manufactured by JAPAN POLYPROPYLENE Co., Ltd., Trade name TAFMER XM, trade name TAFTHREN manufactured by Sumitomo Chemical Co., Ltd., and trade name LMPO manufactured by IDEMITSU RETAIL MARKETING Co., Ltd.

The maleic acid modified polyolefin resin (B) has a non-polar polyolefin skeleton. Therefore, the primer layer 3 can have high adhesion with non-polar materials such as polyolefin. Further, the maleic acid modified polyolefin resin (B) is modified by at least one of maleic acid and maleic anhydride, and therefore has a polar portion. 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) to the maleic acid modified polyolefin resin (B) is preferably within a range of 80:20 to 20:80. In this case, the primer layer 3 can have particularly high adhesion to non-polar materials such as polyolefin.

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

The primer composition may contain water (C) and a hydrophilic organic solvent 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, ethylcellulose, and dicellulose; and ketones such as cyclohexanone. When the primer composition contains a hydrophilic organic solvent, the amount of the hydrophilic organic solvent is preferably within a range of 0.1 to 50% by mass based on the total amount of water (C) and the hydrophilic organic solvent.

The primer composition may also contain a leveling agent. For example, when the primer composition contains a hydrophilic organic solvent such as alcohols and glycol ethers, the hydrophilic organic solvent can function as a leveling agent.

The primer composition may contain a crosslinking agent. The cross-linking agent can contain, for example, at least one selected from the group consisting of: oxazoline Crosslinking agent, carbodiimide crosslinking agent, isocyanate crosslinking agent, epoxy crosslinking agent.

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

The primer composition may further contain suitable additives such as a defoamer, a film-forming aid, a pigment, and a dye.

The manufacturing method of the primer composition of this embodiment is a method of manufacturing a primer composition containing a polymerization reaction product (A), a maleic acid modified polyolefin resin (B), And water (C), and the method includes the step of emulsifying and polymerizing the ethylenically unsaturated monomer (b) in a mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b), Thereby, the polymerization reaction product (A) was synthesized; and the polymerization reaction product (A) was mixed with the maleic acid-modified polyolefin resin (B). This production method includes, for example, the steps of synthesizing a polymerization reaction product (A) by emulsifying and polymerizing a nonionic ethylenically unsaturated monomer (b) using a saturated polyester resin (a) as an emulsifier; and, The aqueous dispersion liquid containing the polymerization reaction product (A) and the maleic acid modified polyolefin resin (B) were mixed.

The method for synthesizing the polymerization reaction product (A) and the method for obtaining an aqueous dispersion containing the polymerization reaction product (A) are as described above. The water in the aqueous dispersion can directly become the water (C) in the primer composition. The amount of water (C) in the primer composition may be further added to the water dispersion liquid.

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, and the primer layer 3 is located on the base material 2. The primer layer 3 contains a dried material of the primer composition. In this embodiment, the laminated member 1 further includes an outer layer 4 which is located on the primer layer 3 and is made of metal or resin. That is, the substrate 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 base material 2 is made of a non-polar material, the adhesion between the base material 2 and the primer layer 3 is high.

The base material 2 is made of a resin such as a thermoplastic resin or a metal such as a steel plate. The substrate 2 is particularly preferably a film made of a thermoplastic resin. Examples of the thermoplastic resin include: polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, poly Polyester resins such as butylene naphthalate; polyhydroxycarboxylic acids such as polyglycolic acid and polylactic acid; aliphatic polyester resins such as polyethylene succinate and polybutyl succinate; nylon 6, nylon 66. Polyamide resins such as nylon 46; polyolefin resins such as polypropylene, polyethylene, and ethylene-vinyl acetate copolymers; polyimide resins; polyarylate resins; and those containing two or more of these resins mixture. The substrate 2 is preferably made of a polyolefin resin, and particularly preferably made of a polypropylene resin.

For example, a primer composition is coated on the substrate 2 and then dried, whereby the primer layer 3 can be produced on the substrate 2.

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.

The polyolefin resin is dried and then melt-extruded to produce an unstretched polyolefin resin sheet. This polyolefin resin sheet is stretched in one direction by a heating roller or the like to produce a uniaxially stretched polyolefin resin film. Further, the uniaxially stretched polyolefin resin film was heated while being extended in a direction perpendicular to the aforementioned direction, and then subjected to heat treatment to complete orientation, thereby producing a biaxially stretched polyolefin resin film.

At any stage in the process of making a biaxially stretched polyolefin resin film, apply a primer composition to an unstretched polyolefin resin sheet, a uniaxially stretched polyolefin resin film, or a biaxially stretched polyolefin resin film. Then, the primer layer 3 can be produced by drying.

For example, the primer layer 3 can be produced by an offline method. That is, after the biaxially stretched polyolefin resin film is produced, the primer composition is coated on the biaxially stretched polyolefin resin film and then dried, whereby the primer layer 3 can be produced.

The primer layer 3 can also be produced by an inline method. That is, the primer layer 3 may be produced in the middle of the process of producing a biaxially stretched polyolefin resin film from a polyolefin resin. At this time, for example, a primer composition is coated on an unstretched polyolefin resin sheet, and then dried to prepare a primer layer 3, and then the unstretched polyolefin resin sheet is pressed in two directions. Sequential stretching and further heat treatment can produce a biaxially stretched polyolefin resin film. In addition, a primer composition is applied to a uniaxially stretched polyolefin resin film, and then dried to prepare a primer. The lacquer layer 3 is then extended with a uniaxially stretched polyolefin resin film and further subjected to a heat treatment, whereby a biaxially stretched polyolefin resin film can also be produced.

In this embodiment, since the primer composition especially contains water (C) as a solvent or a dispersion medium, the organic solvent does not volatilize during the process of making the primer layer 3 from the primer composition, or the amount of organic solvent volatilization Get suppressed. Therefore, in the process of producing a biaxially stretched polyolefin resin film from a polyolefin resin, the risk of ignition of an organic solvent due to heat during stretching and heat treatment is low. Therefore, in any of the offline method and the in-line method, the risk of fire can be suppressed, and the primer layer 3 can be produced from the primer composition.

In addition, if the primer composition contains water (C) as a solvent or a dispersion medium, it is difficult for the organic solvent to be released from the primer composition to the environment, so it is friendly to the environment.

On the primer layer 3, an outer layer 4 can be made. The outer layer 4 is made of a suitable resin or a suitable metal. The outer layer 4 is, for example, the following layers: a photographic photosensitive layer; a diazo photosensitive layer; a matte layer; a magnetic layer; an inkjet ink receiving layer; a hard coating layer; a coating layer; a UV-curing resin, a thermosetting resin, Layers composed of printing ink, UV ink, etc .; Adhesive layers formed by dry lamination or extrusion lamination; Vacuum evaporation layers composed of metal, inorganic substances or oxides thereof; Electron beam evaporation, sputtering Thin films formed by ion plating, ion plating, chemical-vapor deposition (CVD) or plasma polymerization Layer; or organic barrier layer. The primer layer 3 can have high adhesion with various outer layers 4 made of resin or metal.

[Example]

(1) Preparation of samples A to G

Samples A to G were prepared as follows, and samples A to G were aqueous dispersions containing a saturated polyester resin.

A reaction vessel having a capacity of 1000 ml was prepared. The reaction vessel was equipped with a stirrer, a nitrogen inlet, a thermometer, a rectification tower, and a condenser. Into this reaction vessel, components other than 1,2-trimellitic anhydride in the column of "raw material components of saturated polyester resin" in Tables 1 and 2 were added to obtain a mixture. The components were heated to 200 ° C while being stirred and mixed in a normal pressure and nitrogen environment, and then gradually heated to 250 ° C over 4 hours, thereby completing the esterification reaction and transesterification reaction. Then, add 1,2,4-trimellitic anhydride in the column of "raw material components of saturated polyester resin" in Table 1 and Table 2 to this mixture, and slowly decompress to 0.67 hPa at a temperature of 230 ° C. (0.5 mmHg), and then maintained in this state for 2 hours, thereby performing a polycondensation reaction to synthesize a saturated polyester resin.

Saturated polyester resin, isopropyl alcohol, 25% ammonia water, and water were added to the container at the mass ratios shown in the "Sample Composition" column of Tables 1 and 2. These components were kept at a temperature of 75 to 85 ° C. for 2 hours while being stirred, thereby obtaining an aqueous dispersion, and the concentration of the saturated polyester resin in the aqueous dispersion was 25% by mass.

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

(2) Preparation of samples A-1 to G-1

Samples A-1 to G-1 were prepared in the following manner, and the samples A-1 to G-1 were aqueous dispersions containing a polymerization reaction product.

Prepare a reaction vessel with a capacity of 2000 ml. The reaction vessel is equipped with a stirrer, a nitrogen inlet, a thermometer, a dropping funnel, and a reflux condenser. To this reaction vessel, the "saturated polyester resin aqueous dispersions" in Tables 3 and 4 are added. The ingredients shown in the "" column are heated to 80 ° C while stirring the ingredients in a nitrogen environment. Next, 2 parts by mass of an ammonium persulfate aqueous solution having a concentration of 5% by mass as a polymerization initiator was added to the reaction vessel, and the contents of the reaction vessel were stirred while being dropped into the reaction vessel over a period of 2 hours. The components shown in the column of "ethylenically unsaturated monomer" in Tables 3 and 4. Then, 2 parts by mass of an ammonium persulfate aqueous solution having a concentration of 5% by mass was added to the reaction container, and the contents of the reaction container were stirred while being maintained at a temperature of 80 ° C. for 3 hours, thereby synthesizing an emulsified polymer.

Furthermore, when the sample B-2 was prepared, 50 parts by mass of an acrylic resin aqueous dispersion liquid having a concentration of 20% by mass was added to the contents of the reaction container. The acrylic resin aqueous dispersion was prepared by mixing 100 parts by mass of an acrylic resin (manufactured by BASF, trade name Joncryl 680), 25 parts by mass of 25% ammonia water, and 375 parts by mass of water while stirring at 75 ~ Hold at 85 ° C for 2 hours.

When preparing sample C-3, 100 parts by mass of a styrene-maleic anhydride copolymer aqueous dispersion was added to the contents of the reaction container at a concentration of 20% by mass. When the sample F-1 was prepared, 50 parts by mass of a styrene-maleic anhydride copolymer aqueous dispersion was added to the contents of the reaction container at a concentration of 20% by mass. The styrene-maleic anhydride copolymer aqueous dispersion was prepared by using 100 parts by mass of a styrene-maleic anhydride copolymer (Cray Valley Company, trade name SMA 1440) and 25% ammonia water. While stirring 25 parts by mass and 375 parts by mass of water, keep it at a temperature of 75 to 85 ° C. for 2 hours.

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

The columns "mass ratio of saturated polyester resin to ethylenically unsaturated monomer" in Tables 3 and 4 show the mass of saturated polyester resin and ethylenically unsaturated monomer in the aqueous dispersion of saturated polyester resin. ratio.

[table 3]

(3) Preparation of sample A-mix

In the following manner, a sample A-mix was prepared.

Prepare a reaction container with a capacity of 1000 ml. The reaction container is equipped with a stirrer, a nitrogen inlet, a thermometer, a dropping funnel, and a reflux condenser. To the reaction container, 240 parts by mass of ion-exchanged water and 5 parts by mass of sodium lauryl sulfate are added. The components were heated to 80 ° C while being stirred in a nitrogen atmosphere. Next, 2 parts by mass of an ammonium persulfate aqueous solution having a concentration of 5% by mass as a polymerization initiator was added to the reaction vessel, and then the contents of the reaction vessel were stirred and dropped into the reaction vessel over a period of 2 hours. 60 parts by mass of methyl methacrylate and 40 parts by mass of butyl methacrylate. Next, 2 parts by mass of an ammonium persulfate aqueous solution having a concentration of 5% by mass was added to the reaction vessel, and the contents of the reaction vessel were stirred while being maintained at a temperature of 80 ° C for 3 hours, thereby preparing water for emulsified polymer. Dispersions.

The aqueous dispersion of the emulsified polymer was mixed with Sample A in the following manner to obtain Sample A-mix: the saturated polyester resin in Sample A and methyl methacrylate used in the synthetic emulsion polymer and The total mass ratio of butyl methacrylate was 1: 1.

(4) Preparation of sample C-mix

In the following manner, a sample C-mix was prepared.

Prepare a reaction container with a capacity of 1000 ml. The reaction container is equipped with a stirrer, a nitrogen inlet, a thermometer, a dropping funnel, and a reflux condenser. To the reaction container, 240 parts by mass of ion-exchanged water and 5 parts by mass of sodium lauryl sulfate are added. The components were heated to 80 ° C while being stirred in a nitrogen atmosphere. Next, 2 parts by mass of an ammonium persulfate aqueous solution with a concentration of 5% by mass was added to the reaction vessel as a polymerization initiator. While stirring the contents of the reaction vessel, 40 mass of methyl methacrylate was added dropwise to the reaction vessel over 2 hours. Parts, 40 parts by mass of butyl methacrylate, and 20 parts by mass of 2-hydroxyethyl methacrylate. Next, 2 parts by mass of an ammonium persulfate aqueous solution having a concentration of 5% by mass was added to the reaction vessel, and the contents of the reaction vessel were stirred while being maintained at a temperature of 80 ° C for 3 hours, thereby preparing water for emulsified polymer. Dispersions.

The aqueous dispersion of the emulsified polymer was mixed with the sample C to obtain a sample C-mix: a saturated polyester resin in the sample C and methyl methacrylate used for the synthetic emulsified polymer, The total mass ratio of butyl methacrylate and 2-hydroxyethyl methacrylate is 3: 2.

(5) Preparation of Examples 1 to 19 and Comparative Examples 1 to 4

Examples 1 to 19 and Comparative Examples 1 to 4 of the primer composition were prepared as follows.

The components shown in the column of "aqueous dispersion liquid containing a polymerization reaction product" in Tables 5 and 6 and the components shown in the column of "modified polyolefin resin solution" are mixed to obtain a mixed solution. In the preparation of Examples 11, 17, and 19, the ingredients shown in "Additives" were also further mixed. To this mixed solution, a 30% by mass butylcellulose aqueous solution was added as a leveling agent, thereby obtaining a primer composition having a solid content concentration of 25% by mass.

The components shown in the "Modified Polyolefin Resin Solution" column in Tables 5 and 6 are aqueous dispersions of maleic acid modified polyolefin resin, and the details are shown below.

‧GENPOLY HGW9566: Manufactured by Lotte Chemical Corporation under the trade name GENPOLY HGW9566. Aqueous dispersion of maleic anhydride modified polypropylene resin. The weight average molecular weight is more than 40,000.

‧AUROREN AE-301: Made by Japan Paper Co., Ltd. under the trade name AUROREN AE-301. Maleic anhydride-acrylic acid Dispersion of high quality polyolefin resin. The weight average molecular weight is 80,000 ~ 100,000.

‧AUROREN AE-501: Made by Japan Paper Co., Ltd. under the trade name AUROREN AE-501. Aqueous dispersion of maleic anhydride modified polyolefin resin, weight average molecular weight 100,000 ~ 1.500000.

‧APTOLOK BW-5550: Made by Mitsubishi Chemical Corporation under the trade name APTOLOK BW-5550. An aqueous dispersion of a copolymer of maleic anhydride modified polypropylene and methoxypoly (oxyethylene / oxypropylene) -2-propylamine. The weight average molecular weight is 135,000.

The details of the components shown in the "Additives" column in Tables 5 and 6 are as follows.

‧EPOCROS WS-700: Water-soluble polymer containing oxazoline group, manufactured by Japan Catalyst Co., Ltd. under the trade name EPOCROS WS-700.

‧CARBODILITE SV-02: Water-based cross-linking agent that imparts a hydrophilic segment to a polycarbodiimide resin, manufactured by Nishinbo Chemical Co., Ltd. under the trade name CARBODILITE SV-02.

(6) Physical property test

The following tests were performed on Examples 1 to 19 and Comparative Examples 1 to 4 of the primer composition.

(6-1) Production of primer layer

Prepare an untreated polypropylene film as the substrate. On the substrate, 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 this haze test, a polyethylene terephthalate film (manufactured by TORAY Co., Ltd., trade name: LUMIRROR T60 # 100) was used as a substrate, and a primer layer having a thickness of 3 μm was formed. Next, the haze meter NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used to measure the haze of the substrate alone and the total haze of the substrate and the primer layer. A value obtained by subtracting the haze of the substrate alone from the total haze of the substrate and the primer layer was calculated as the haze of the primer layer.

(6-3) Normal temperature viscosity

An untreated polypropylene film is prepared as a component of a primer layer superposed on a substrate. In a state where the member is overlapped with the primer layer, the member and the primer layer are bonded under conditions of a temperature of 25 ° C., a humidity of 60%, an applied pressure of 0.1 MPa, and a compression bonding time of 1 hour. Then, the adhesion between the primer layer and the component at normal temperature was confirmed. As a result, the case where adhesion was not confirmed at the interface between the primer layer and the component was evaluated as "A", the case where adhesion was confirmed at a part of the interface was evaluated as "B", and the case where viscosity was confirmed at most of the interface Evaluation is "C".

(6-4) Substrate adhesion

The cellophane adhesive tape was closely adhered to the primer layer on the substrate, and then peeled off to observe the condition of the remaining primer layer. As a result, the case where peeling of the primer layer could not be confirmed was evaluated as "A", the case where peeling was confirmed on a very small portion of the primer layer was evaluated as "B", and peeling was confirmed on a part of the primer layer. The case where it was separated was evaluated as "C", and the case where peeling was confirmed in most of the primer layer was evaluated as "D".

(6-5) Adhesiveness of coating layer

On the primer layer on the substrate, an acrylic resin-based water-based white coating was applied using a bar coater, and then heated at 120 ° C. for 5 minutes. Thereby, a coating layer having a thickness of 2 μm was formed on the primer layer. The cellophane adhesive tape was brought into close contact with the coating layer and then peeled off, and the condition of the remaining coating layer was observed. As a result, the case where peeling of the coating layer could not be confirmed was evaluated as "A", the case where peeling was confirmed on a very small portion of the coating layer was evaluated as "B", and the case where peeling was confirmed on a part of the coating layer was evaluated as "C". ", And the case where peeling was confirmed in most of the coating layers was evaluated as" D ".

(6-6) Adhesiveness of aluminum vapor deposition layer

An aluminum vapor-deposited layer having a thickness of about 1 μm is formed on the primer layer on the substrate through a vacuum evaporation step. The cellophane adhesive tape was brought into close contact with the aluminum vapor-deposited layer and then peeled off, and the condition of the remaining aluminum vapor-deposited layer was observed. As a result, the case where peeling of the aluminum vapor-deposited layer could not be confirmed was evaluated as "A", the case where peeling was confirmed on a very small part of the aluminum vapor-deposited layer was evaluated as "B", and the case where peeling was confirmed on part of the aluminum-evaporated layer was evaluated It was "C", and the case where peeling was confirmed in most of the aluminum vapor deposition layers was evaluated as "D".

As can be seen from the embodiment described above, the primer composition of 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 an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b). product. The saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

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

In the primer composition of the third aspect, in the first or second aspect, the saturated polyester resin (a) has a polycarboxylic acid residue (a1) and a diol residue (a2), and the polycarboxylic acid The residue (a1) contains a polycarboxylic acid residue (a11) of 3 or more members, and the amount of the polycarboxylic acid residue (a11) is within the range of 1 to 50 mole% relative to the polycarboxylic acid residue (a1). .

In the fourth aspect of the primer composition, in the third aspect, the polycarboxylic acid residue (a1) contains an alicyclic polycarboxylic acid residue (a10), and compared to the polycarboxylic acid residue (a1), The amount of the alicyclic polycarboxylic acid residue (a10) is in the range of 30 to 99 mole%.

In the primer composition of the fifth aspect, in the third or fourth aspect, the diol residue (a2) contains an alicyclic diol residue (a20), and compared to the diol residue (a2), The amount of the alicyclic diol residue (a20) is in the range of 30 to 100 mole%.

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

In the primer composition of the seventh aspect, in the first to sixth aspects, the nonionic ethylenically unsaturated monomer (b1) contains a monomer having a hydroxyl group. (b0) 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 mole%.

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

The laminated member of the ninth aspect is the eighth aspect. The laminated member includes an outer layer, which is located on the primer layer and is made of metal or resin.

The tenth aspect of the method for producing a primer composition is a method for producing a primer composition including a polymerization reaction product (A), a maleic acid modified polyolefin resin ( B), and water (C). This production method includes the steps of synthesizing a polymerization reaction product (e.g., by emulsifying and polymerizing an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b)). 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 in the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

In the eleventh aspect, the method for producing a primer composition is the tenth aspect, wherein the saturated polyester resin (a) has a polycarboxylic acid residue (a1) and a diol residue (a2), and the polycarboxylic acid The residue (a1) contains a polybasic carboxylic acid residue (a11) of 3 or more members, and the amount of the polybasic carboxylic acid residue (a11) is 1 to 50 mol% relative to the polycarboxylic acid residue (a1). Within range.

Claims (11)

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 saturating a polymer A product of emulsification polymerization of the aforementioned ethylenically unsaturated monomer (b) in a mixture of an ester resin (a) and an ethylenically unsaturated monomer (b). The saturated polyester resin (a) has 10 to 100 mg of KOH. The acid value in the range of / g is that the ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1). The primer composition according to claim 1, wherein a mass ratio of the polymerization reaction product (A) to the maleic acid modified polyolefin resin (B) is in a range of 80:20 to 20:80 Inside. The primer composition according to claim 1 or 2, wherein the saturated polyester resin (a) has a polycarboxylic acid residue (a1) and a diol residue (a2), and the polycarboxylic acid residue Group (a1), which contains a polyvalent carboxylic acid residue (a11) of 3 or more members, and the amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is 1 to 50 mole% Within range. The primer composition according to claim 3, wherein the polycarboxylic acid residue (a1) contains an alicyclic polycarboxylic acid residue (a10), and the polycarboxylic acid residue (a1) contains The amount of the alicyclic polycarboxylic acid residue (a10) is in the range of 30 to 99 mole%. The primer composition according to claim 3, wherein the diol residue (a2) contains an alicyclic diol residue (a20), and the alicyclic type is relative to the diol residue (a2). The amount of the diol residue (a20) is in the range of 30 to 100 mole%. The primer composition according to claim 1 or 2, wherein the mass ratio of the saturated polyester resin (a) to the ethylenically unsaturated monomer (b) is in the range of 99: 1 to 10:90 . The primer composition according to claim 1 or 2, wherein the nonionic ethylenically unsaturated monomer (b1) contains a monomer (b0) having a hydroxyl group, and the ethylenically unsaturated monomer (b0) contains b) The amount of the aforementioned monomer (b0) having a hydroxyl group is in the range of 1 to 40 mole%. A laminated member comprising a base material and a primer layer, wherein the primer layer is located on the base material, and the primer layer contains a dried substance of the primer composition according to claim 1 or 2. The laminated member according to claim 8, wherein the laminated member includes an outer layer, and the outer layer is located on the primer layer and is made of metal or resin. A method for manufacturing a primer composition, wherein the primer composition contains a polymerization reaction product (A), a maleic acid modified polyolefin resin (B), and water (C), and the manufacturing method includes the following steps: The aforementioned ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b) is subjected to emulsion polymerization to synthesize the aforementioned polymerization reaction product (A); and, The polymerization reaction product (A) is mixed with the maleic acid modified polyolefin resin (B); and the saturated polyester resin (a) has an acid value in a range of 10 to 100 mgKOH / g, and the ethylene The unsaturated unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1). The method for producing a primer composition according to claim 10, wherein the saturated polyester resin (a) has a polycarboxylic acid residue (a1) and a diol residue (a2), and the polycarboxylic acid The residue (a1) contains a polycarboxylic acid residue (a11) having a valence of 3 or more, and the amount of the polycarboxylic acid residue (a11) is 1 to 50 moles relative to the polycarboxylic acid residue (a1). Within the range of%.