TW202204562A - Adhesive and multilayer body - Google Patents

Abstract

This adhesive contains a thermoplastic resin binder (A), modified polyolefin resin particles (B) and an organic solvent. This adhesive has high water repellency, while exhibiting high bondability with respect to metals, resins and the like. Since this adhesive does not contain, as an essential ingredient, hydrophobic inorganic particles, this adhesive is easy to blend during the production of a multilayer body or a packaging material, and enables a blended liquid to have high stability.

Description

Adhesives and Laminates

The present invention relates to an adhesive and a laminate, and more specifically, to an adhesive and laminate having high water repellency and high adhesion to metals, resins, and the like.

Various materials are known as packaging materials, and the contents thereof include, for example, jelly-like desserts, puddings, yogurt, liquid lotions, toothpaste, curry bars, syrups, petroleum jelly, face cream, face mousse, etc. Food, beverages, pharmaceuticals, cosmetics, chemicals, etc. The properties of the contents are also diverse, such as solid, semi-solid, liquid, viscous, and gel.

Packaging materials used to package such contents require thermal adhesion, light shielding properties, heat resistance, durability, etc., in addition to sealing properties, in accordance with the contents, packaging form, and application. However, even a packaging material satisfying these characteristics still has the following problems. That is, there is a problem that the contents adhere to the packaging material. If the content adheres to the packaging material, it is difficult to completely use up the content, resulting in waste. Furthermore, in order to completely use up the contents, the contents adhering to the packaging material must be collected separately, which takes a lot of procedures. Therefore, in addition to the above-mentioned sealing properties, the packaging material must have the property that the contents are not easily attached to the packaging material, that is, non-adhesive properties.

Furthermore, for lids of containers for food, medicine, and cosmetics, high adhesion to metals such as aluminum foil, resins such as polypropylene, and materials such as paper is required. Patent Document 1 describes a layered product in which hydrophobic oxide fine particles with an average primary particle diameter of 3 to 100 nm are adhered to at least a part of the surface of a layer containing a thermoplastic resin, and a filler particle system containing at least one of an organic component and an inorganic component. contained in the layer containing the above-mentioned thermoplastic resin.

Patent Document 2 describes a cover material including a base material, a heat-sealing layer, and an anti-adhesion layer for preventing adhesion of contents in this order, wherein the heat-sealing layer is a resin composition obtained by blending natural rubber or synthetic rubber with a heat-sealing resin. In the heat-sealing layer, the content of natural rubber or synthetic rubber is 10 to 50% by mass, and the anti-adhesion layer contains hydrophobic fine particles with a particle diameter of 1.0 μm or less.

Patent Document 3 describes a cover material for preventing contents adhesion, which has at least a base material layer and a heat-sealing layer, and an adhesion-preventing layer on the outer surface of the heat-sealing layer, and the adhesion-preventing layer is made of hydrophobic inorganic fine particles and modified with It is composed of a mixture of binders with polyolefin resin as the main component.

Patent Document 4 describes a packaging sheet comprising a base film and a heat seal layer laminated on at least one side of the base film, wherein the heat seal layer contains a heat sealant and polyolefin-based particles, and is combined with the base film. The surface roughness Ra of the surface on the opposite side is 1.00 to 7.00 μm, the average particle diameter D50 of the polyolefin-based particles is 10 to 50 μm, and the melting point is 100 to 180°C. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5674221 Patent Document 2: Japanese Patent Laid-Open No. 2019-14493 Patent Document 3: Japanese Patent No. 5848058 Patent Document 4: International Patent No. WO2018/003978

(The problem that the invention intends to solve)

Since the laminated bodies or the cover materials described in Patent Documents 1 to 3 have hydrophobic inorganic particles in the surface layer, they exhibit non-adhesion and water repellency. However, since this hydrophobic inorganic particle is bulky and easily scattered, it may be difficult to prepare it when manufacturing a layered product or a cover material. Moreover, since the hydrophobic inorganic particles are fine particles, there is also a problem that the stability of the preparation solution containing the hydrophobic inorganic particles is low.

The packaging sheet described in Patent Document 4 contains polyolefin-based particles in the surface layer and forms irregularities in the surface layer to express non-adhesion, but this packaging sheet cannot obtain sufficient non-adhesion and adhesive strength.

In addition, in the inventions described in Patent Documents 1 to 3, it is difficult to achieve high adhesion to materials such as metals such as aluminum foil and resins such as polypropylene. An object of the present invention is to provide an adhesive having high water repellency and high adhesion to metals, resins, etc., and a laminate using the adhesive. (Technical means to solve problems)

The present invention which achieves the above-mentioned object relates to, for example, the following [1] to [11]. [1] An adhesive comprising a thermoplastic resin binder (A), modified polyolefin resin particles (B), and an organic solvent. [2] The adhesive according to [1], wherein the water contact angle of the dry coating film of the adhesive is 110∘ or more. [3] The adhesive according to [1] or [2], wherein the volume-based cumulative 50% particle size (D50) of the modified polyolefin resin particles (B) is 1 to 1000 μm. [4] The adhesive according to any one of [1] to [3], wherein the volume-based cumulative 90% particle size (D90) in the modified polyolefin resin particles (B) is a ratio (D90) to D50 /D50) is 1.1~4.0. [5] The adhesive according to any one of [1] to [4], wherein the thermoplastic adhesive (A) contains a resin selected from the group consisting of acrylic resins, styrene-based resins, ABS resins, vinyl chloride resins, and polyethylene resins , polypropylene resin, polybutene resin, polyamide resin, polycarbonate, polyacetal, fluorine resin, silicone resin and polyester resin and at least one thermoplastic resin of these modified resins. [6] The adhesive according to any one of [1] to [5], wherein the solid content weight ratio (A/B) of the thermoplastic binder (A) and the modified polyolefin resin particles (B) 80/20~5/95. [7] The adhesive according to any one of [1] to [6], further comprising hydrophobic inorganic particles. [8] A laminate comprising a base material and an adhesive layer laminated on at least one surface of the base material, wherein the base material is resin or metal, and the adhesive agent layer is any one of [1] to [7] A layer obtained by an adhesive. [9] The laminate according to [8], wherein the water contact angle of the adhesive layer is 110∘ or more. [10] The laminate according to [8] or [9], wherein the adhesive layer is a heat-sealing layer. [11] A packaging material comprising the laminate of any one of [8] to [10]. (Compared to the efficacy of the prior art)

The adhesive of the present invention has high water repellency and high adhesion to metals or resins. Since the adhesive agent of the present invention does not contain hydrophobic inorganic particles as an essential component, it is easy to prepare a layered product or a packaging material, and the stability of the preparation solution is high.

Since the adhesive layer composed of the adhesive of the present invention exhibits functions such as water repellency and adhesiveness as a single layer, the number of steps in manufacturing the packaging material can be reduced. In the adhesive of the present invention, since all the adhesive components contained in the adhesive can be made of adhesive resin, high adhesive force can be realized. Since the modified polyolefin resin particles contained in the adhesive have the dual effect of water repellency and adhesiveness, water repellency and adhesiveness can still be achieved even if other components are not compounded.

[adhesive] The adhesive of the present invention contains a thermoplastic resin binder (A), modified polyolefin resin particles (B), and an organic solvent.

The thermoplastic resin adhesive (A) is a component that imparts adhesiveness to the adhesive of the present invention. As a thermoplastic resin binder (A), an olefin resin (a-1), a styrene resin (a-2), etc. are mentioned, for example. Moreover, as a thermoplastic resin binder (A), the mixture which mixed the olefin resin (a-1) and the styrene resin (a-2) in arbitrary ratios can also be used.

In addition, one of the preferable forms of the thermoplastic resin binder (A) is a modified thermoplastic resin in which a part or all of the binder is modified by grafting with a polar group-containing monomer. In addition, the measurement conditions will be described in detail below, and one of the preferable forms is that the heat of fusion of the thermoplastic resin binder (A) is 0 J/g or more and 40 J/g or less.

The thermoplastic resin binder (A) may be one type or two or more types. As the thermoplastic resin binder (A), it is preferable to use an olefin-based resin (a-1) and a styrene-based resin (a-2). In addition, it is also preferable to use a modified olefin-based resin graft-modified with a polar group-containing monomer and a modified styrene-based resin graft-modified with a polar group-containing monomer.

<Olefin-based resin (a-1)> Examples of the olefin-based resin (a-1) include a polymer (a-1a) derived from an α-olefin having 2 to 20 carbon atoms, and an unmodified polymer derived from an α-olefin having 2 to 20 carbon atoms. The polymer is preferably a modified polymer (a-1b) modified by grafting with a polar group-containing monomer.

[Polymer (a-1a) derived from α-olefin having 2 to 20 carbon atoms] The polymer (a-1a) is not particularly limited as long as it contains a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and may be a polymer consisting of an α-olefin having 4 to 20 carbon atoms, or Copolymers obtained by using α-olefins having 4 to 20 carbon atoms and α-olefins having 2 to 3 carbon atoms may also contain unsaturated monomers other than α-olefins (hereinafter also referred to as "other unsaturated monomers") if necessary. A polymer of constituent units derived from monomer (3)").

The α-olefin used as the raw material of the polymer (a-1a) may be used alone or in combination of two or more. That is, the above-mentioned polymer (a-1a) may be a homopolymer of an α-olefin having 2 to 20 carbon atoms, a copolymer obtained by using the α-olefin, or one or more carbon atoms may be used. A copolymer (a-1a1) obtained from 4 to 20 α-olefins and one or more kinds of α-olefins with 2 to 3 carbon atoms.

As a copolymer (a-1a1), a random copolymer and a block copolymer are mentioned, for example, Preferably it is a random copolymer. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Linear or branched α-olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

The above-mentioned α-olefin having 4 to 20 carbon atoms is preferably a linear olefin having 4 to 10 carbon atoms, from the viewpoint of easily obtaining a polymer having excellent solubility in organic solvents and strength, and more preferably A linear olefin having 4 to 6 carbon atoms; from the viewpoint of obtaining a polymer having particularly excellent effects as described above, it is more preferable to contain 1-butene, and particularly preferably 1-butene.

Examples of the α-olefin having 2 to 3 carbon atoms include ethylene and propylene. From the viewpoint of easily obtaining a polymer excellent in solubility in organic solvents and strength, propylene is preferably contained, and propylene is particularly preferred. .

As the other unsaturated monomer (3), for example, the same conjugated dienes, non- Conjugated polyenes.

The polymer (a-1a) is preferably a copolymer (a-1a1), more preferably a propylene and a carbon number of 4 to 20, from the viewpoint of easily obtaining a polymer excellent in solubility to a solvent and strength. The copolymer of the α-olefin is more preferably a copolymer in which all the structural units other than the structural unit derived from propylene are the above-mentioned structural units derived from α-olefin having 4 to 20 carbon atoms, and more preferably the above-mentioned carbon The α-olefins of numbers 4 to 20 are 1-butene, especially the copolymer of 1-butene and propylene.

In the polymer (a-1a), the content ratio of the constituent units derived from α-olefins having 4 to 20 carbon atoms is 100 mol% relative to the constituent units derived from α-olefins having 2 to 20 carbon atoms. Preferably, it is, for example, 5 mol % or more, preferably 10 mol % or more, more preferably 20 mol % or more, relative to 100 mol % of the total constituent units constituting the polymer (a-1a); and, for example, 100 mol % or more. Molar % or less, preferably 60 mol % or less, more preferably 50 mol % or less, still more preferably 40 mol % or less, and particularly preferably 35 mol % or less.

If the content ratio of the constituent units derived from α-olefins having 4 to 20 carbon atoms satisfies the above upper limit, a polymer with better strength can be obtained, and when the above lower limit is satisfied, a polymer with better solubility in organic solvents can be obtained. body.

In the copolymer (a-1a), the content ratio of constituent units derived from α-olefins having 2 to 3 carbon atoms (preferably propylene) is relative to the constituent units derived from α-olefins having 2 to 20 carbon atoms. 100 mol %, preferably 100 mol % relative to the total constituent unit constituting the copolymer (a-1a), preferably 40 mol % or more, more preferably 50 mol % or more, and more preferably 60 mol % % or more, particularly preferably 65 mol % or more, and more preferably 95 mol % or less, more preferably 90 mol % or less, and still more preferably 80 mol % or less.

If the content ratio of structural units derived from α-olefins having 2 to 3 carbon atoms satisfies the above upper limit, the melting point (Tm) and the heat of fusion (ΔH) of the obtained polymer can be lowered, and if the above lower limit is satisfied, the strength can be obtained. more superior polymers.

The heat of fusion (ΔH) of the polymer (a-1a) is preferably 0 J/g or more, more preferably 3 J/g or more, particularly preferably 5 J/g or more, and more preferably 40 J/g or less, more preferably 35 J/g g or less. In addition, when ΔH is 0 J/g, that is, when ΔH is not observed, it is also one of the preferable forms.

The polymer (a-1a) having the above ΔH can be obtained, for example, by appropriately adjusting the content ratio of the constituent unit derived from the α-olefin having 2 to 3 carbon atoms in the polymer (a-1a).

If ΔH satisfies the above-mentioned upper limit, the adhesive of the present invention has excellent adhesive strength after thermocompression bonding. In the present invention, ΔH is determined by differential scanning calorimetry (DSC measurement) in accordance with JIS K 7122. Specifically, it was calculated from the peak area of the heat pattern obtained during the temperature increase process of 10°C/min. More specifically, in order to cancel the thermal history before the measurement, the temperature was raised to 200°C at 10°C/min before the measurement, held at this temperature for 3 minutes, then lowered to 0°C at 10°C/min, and kept at this temperature. After 3 minutes, ΔH was measured.

The melting point (Tm) of the polymer (a-1a) is preferably less than 120°C, more preferably less than 100°C. Moreover, the case where Tm is 0 degreeC or more and is not observed is also one of preferable forms. The polymer (a-1a) having the above-mentioned Tm can be obtained, for example, by appropriately adjusting the content ratio of the structural unit derived from the α-olefin having 2 to 3 carbon atoms in the polymer (a-1a).

If Tm satisfies the above-mentioned conditions, even if an adhesive layer is formed from the adhesive of the present invention under low-temperature aging conditions, an adhesive layer with excellent adhesive strength can be obtained. In the polymer (a-1a), the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC) is preferably 1×10 ⁴ or more, and more preferably 1×10 ⁷ or less; the molecular weight distribution (Mw/Mn) is preferably 1 or more, and more preferably 3 or less.

If Mw or Mw/Mn satisfies the above-mentioned lower limit, an adhesive layer with sufficiently high adhesion strength can be obtained, and the adhesive layer and the adherend have good adhesion strength; if the above-mentioned upper limit is satisfied, the dissolution of organic solvents can be obtained A polymer with good properties can be used to obtain an adhesive that is not prone to curing and precipitation.

The above-mentioned polymer (a-1a) can be obtained by polymerizing α-olefin having 2 to 20 carbon atoms in the presence of a known solid Ti catalyst or two metallocene catalysts commonly used in the production of α-olefin polymers. and obtained. Examples of the metallocene catalyst include metallocene compounds containing rac-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, methyl A catalyst for organoaluminum oxy compounds such as alumoxane and organoaluminum compounds such as triisobutylaluminum. More specifically, the above-mentioned polymer (a-1a) can be obtained, for example, by the method described in International Patent Publication No. 2004/87775.

[Modified polymer (a-1b)] As the thermoplastic resin binder (A), a part or all of the above-mentioned unmodified polymer (a-1a) is a modified polymer (a-1b) modified by grafting with a polar group-containing monomer. It is also one of the better forms. If the above-mentioned modified polymer (a-1b) is a polymer obtained by graft-modifying an unmodified polymer derived from an α-olefin having 2 to 20 carbon atoms by a polar group-containing monomer, it is not particularly limited. However, it is preferably a polymer obtained by reacting one or more kinds of monomers having a polar group-containing monomer and one or more kinds of the above-mentioned unmodified polymers.

Specific examples and forms of polar groups in the modified polymer (a-1b), as well as specific examples and preferred forms of polar group-containing monomers are described in the modified polyolefin resin particles (B) described later. The description of the polar group and the polar group-containing monomer is the same.

The ΔH of the modified polymer (a-1b) is preferably 0J/g or more, more preferably 3J/g or more, particularly preferably 5J/g or more, and more preferably 40J/g or less, more preferably 35J/g or less, Excellent below 30J/g. In addition, when ΔH is 0 J/g, that is, when ΔH is not observed, it is also one of the preferable forms.

If ΔH of the modified polymer (a-1b) satisfies the above-mentioned upper limit, the adhesive layer composed of the adhesive of the present invention is excellent in adhesive strength after thermocompression bonding. The modified polymer (a-1b) having the above-mentioned ΔH can be obtained, for example, by appropriately adjusting the content ratio of the structural unit derived from the α-olefin having 2 to 3 carbon atoms in the modified polymer (a-1b). get.

The Tm of the modified polymer (a-1b) is preferably less than 120°C, more preferably less than 100°C, more preferably 90°C or less, particularly preferably 87°C or less, and more preferably 40°C or more, More preferably, it is 50°C or higher. Moreover, the case where Tm is 0 degreeC or more and is not observed is also one of preferable forms.

If the Tm of the modified polymer (a-1b) satisfies the above-mentioned upper limit or the melting point is 0°C or higher and is not observed, the adhesive layer composed of the adhesive of the present invention is the adhesive layer after thermocompression bonding at low temperature. Then the strength is superior.

The modified polymer (a-1b) having the above-mentioned Tm can be obtained, for example, by appropriately adjusting the content ratio of the structural unit derived from the α-olefin having 2 to 3 carbon atoms in the modified polymer (a-1b).

The semi-crystallization time of the modified polymer (a-1b) at 50°C is preferably 100 seconds or more, more preferably 150 seconds or more, and still more preferably 200 seconds or more. In addition, the above-mentioned semi-crystallization time also includes a case where crystallization does not substantially occur, or the value of the semi-crystallization time is too large to be obtained, that is, the semi-crystallization time becomes infinite.

If the semi-crystallization time of the modified polymer (a-1b) satisfies the above-mentioned lower limit, the component of the modified polymer (a-1b) containing the adhesive of the present invention penetrates into the unevenness of the surface of the adherend, and the anchoring effect , the adhesive strength of the obtained adhesive layer can be further improved.

The above-mentioned semi-crystallization time can be obtained by measuring isothermal crystallization by a differential scanning calorimeter. The Mw of the modified polymer (a-1b) measured by GPC in terms of standard polystyrene is preferably 1×10 ⁴ or more, more preferably 2×10 ⁴ or more, particularly preferably 3×10 ⁴ or more, Moreover, it is preferably 1×10 ⁷ or less, more preferably 1×10 ⁶ or less, and particularly preferably 5×10 ⁵ or less.

If the Mw of the modified polymer (a-1b) satisfies the above lower limit, the adhesive layer of the present invention can easily obtain an adhesive layer with excellent bonding strength with the adherend; Modified polymer (a-1b) with good solubility, hard to cure and precipitation. In particular, when the Mw of the modified polymer (a-1b) is 5×10 ⁵ or less, an adhesive layer with better adhesion strength to the adherend can be obtained.

The Mw/Mn of the modified polymer (a-1b) is preferably 1 or more, more preferably 1.5 or more, more preferably 3 or less, more preferably 2.5 or less. If Mw/Mn satisfies the above-mentioned lower limit, a modified polymer (a-1b) with good solubility in organic solvents and less solidification and precipitation can be obtained; if the above-mentioned upper limit is satisfied, the adhesive of the present invention can obtain sufficient adhesive strength Adhesive layer with high adhesion strength to the adherend.

The dynamic viscosity of the modified polymer (a-1b) at 40°C is preferably over 500,000 cSt. Here, when the dynamic viscosity exceeds 500,000 cSt, the fluidity is low and the dynamic viscosity cannot be measured.

In the present invention, the dynamic viscosity at 40°C is measured according to ASTM D445. In the modified polymer (a-1b), the content ratio (modified mass) of the constituent units derived from the polar group-containing monomer is 100% by mass relative to the total constituent units of the modified polymer (a-1b) Preferably it is 0.1 mass % or more, more preferably 0.5 mass % or more, and more preferably 15 mass % or less, more preferably 10 mass % or less, still more preferably 5 mass % or less, particularly preferably 4 mass % or less, still more preferably 2 mass % or less.

If the quality is changed to the above range, the affinity of the adhesive layer obtained from the adhesive of the present invention to the adherend can be improved, so that the bonding strength between the adhesive layer and the adherend can be further improved. As a method for producing a modified polymer (a-1b) by graft-copolymerizing a polar group-containing monomer to an unmodified polymer derived from an α-olefin having 2 to 20 carbon atoms, for example, it will be described later. In the modified polyolefin resin particle (B), the method of graft-copolymerizing the polar group-containing monomer with respect to the raw material polyolefin-based resin is the same as the method. In addition, the modified polymer (a-1b) can also be synthesized in accordance with, for example, a conventional method disclosed in International Patent Publication No. 2017/126520.

<Styrene resin (a-2)> There are no particular limitations on the type and production method of the styrene-based resin (a-2), and examples thereof include copolymers containing structural units derived from monovinylaromatic hydrocarbons such as styrene.

As the styrene-based resin (a-2), for example, a copolymer having a monovinyl-substituted aromatic hydrocarbon (styrene-based aromatic hydrocarbon) as a copolymerization component may be mentioned; as a specific example, styrene-ethylene may be mentioned -Butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butene-butadiene-styrene block copolymer (SBBS) , styrene-butadiene rubber (SBR), styrene-isoprene (SIR), styrene-ethylene copolymer, styrene-butadiene-styrene copolymer (SBS), styrene-isoprene Diene-styrene copolymer (SIS), poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) (α-MeSBα-MeS), poly(α-methylbenzene) ethylene)-polyisoprene-poly(α-methylstyrene) (α-MeSIα-MeS). Furthermore, for example, the conjugated diene part which comprises these copolymers, and specifically, the copolymer which hydrogenated the structural unit derived from butadiene or isoprene is mentioned. Among these, SEBS and SEPS are preferable.

As the styrene-based resin (a-2), it is also one of the preferred embodiments to use a modified styrene-based resin modified by grafting with a polar group-containing monomer. This modification can be performed according to a conventionally known method. The specific example and form of the polar group in the modified styrene-based resin are the same as the description of the polar group and the polar group-containing monomer of the modified polymer (a-1b).

As a polar group-containing monomer which graft-modifies a styrene resin, the polar group-containing monomer described in the modified polymer (a-1b) is mentioned, for example. Among these, unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is preferable, unsaturated carboxylic acid anhydride is more preferable, and maleic anhydride is still more preferable.

In the modified styrene-based resin, the content ratio (modified mass) of the constituent units derived from the polar group-containing monomer is 100 mass % relative to the total constituent units of the modified styrene-based resin, preferably 0.1 mass % or more , more preferably 0.5 mass % or more, and more preferably 15 mass % or less, more preferably 10 mass % or less, still more preferably 5 mass % or less, particularly preferably 4 mass % or less, still more preferably 3 mass % or less.

As a modified styrene resin, a commercial item can also be used. As a specific example of this commercial item, DYNARON 8630P (made by JSR (Example)) and Tuftec M1913 (made by Asahi Kasei Co., Ltd.) are mentioned, for example.

The ΔH of the styrene-based resin (a-2) is preferably 0 J/g or more and 40 J/g or less, and ΔH is 0 J/g (ie, ΔH is not observed), which is also one of the preferred embodiments.

If the ΔH of the styrene resin (a-2) satisfies the above conditions, even if an adhesive layer is formed from the adhesive of the present invention under low temperature aging conditions, an adhesive layer with excellent adhesive strength can be obtained, and an adhesive layer with excellent adhesive strength can be easily obtained. agent layer.

The Tm of the styrene-based resin (a-2) is preferably not observed at 0°C or higher. If the Tm of the styrene-based resin (a-2) satisfies the above-mentioned conditions, even if the adhesive layer is formed by the adhesive of the present invention under low-temperature aging conditions, the decrease in the adhesive strength can be prevented. An adhesive layer excellent in adhesive strength and durability can be obtained.

In the styrene resin (a-2), the Mw in terms of standard polystyrene measured by GPC is preferably 1×10 ⁴ or more, more preferably 2×10 ⁴ or more, particularly preferably 3×10 ⁴ or more, Moreover, it is preferably 1×10 ⁷ or less, more preferably 1×10 ⁶ or less, and particularly preferably 5×10 ⁵ or less.

If the Mw of the styrene resin (a-2) satisfies the above-mentioned lower limit, the adhesive layer of the present invention can easily obtain a sufficiently high adhesive strength, or an adhesive layer with excellent adhesion strength to the adherend; if the above-mentioned upper limit is satisfied, A styrene-based resin (a-2) that has good solubility in organic solvents and is less likely to be cured and precipitated can be obtained. In particular, when the Mw of the styrene-based resin (a-2) is 5×10 ⁵ or less, an adhesive layer with better adhesion strength to the adherend can be obtained.

Mw/Mn of the styrene resin (a-2) is preferably 1 or more, more preferably 1.5 or more, more preferably 3 or less, more preferably 2.5 or less. If Mw/Mn satisfies the above-mentioned lower limit, a styrene resin (a-2) with good solubility in organic solvents and less curing and precipitation can be obtained; if the above-mentioned upper limit is satisfied, the adhesive strength of the present invention can be obtained Adhesive layer with sufficiently high adhesion strength to the adherend.

The modified polyolefin resin particle (B) is a component which imparts water repellency and adhesiveness to the adhesive of the present invention. The modified polyolefin resin particles (B) are particles of a modified polyolefin resin obtained by graft-modifying the polyolefin resin (b) with a polar group-containing monomer.

As a polyolefin resin (b), an ethylene homopolymer, an ethylene copolymer, a propylene homopolymer, a propylene copolymer etc. are mentioned, for example. Among these, it is preferably selected from: ethylene/α-olefin copolymer (b-1); and at least one selected from the group consisting of propylene homopolymer, propylene/ethylene copolymer and propylene/α-olefin copolymer 1 type of propylene-based polymer (b-2); at least one type of constituted group.

The above-mentioned ethylene/α-olefin copolymer (b-1) includes a structural unit derived from ethylene and a structural unit derived from an α-olefin. The α-olefin is preferably an α-olefin having 3 or more carbon atoms, and more preferably an α-olefin having 3 to 50 carbon atoms.

Examples of the α-olefin having 3 to 50 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1-pentene ene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl- 4-Methyl-1-pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc.

The constituent unit derived from ethylene contained in the ethylene/α-olefin copolymer (b-1) is preferably 50 mol % or more and 97 mol % or less, more preferably 60 mol % or more and 95 mol % or less. Further, the constituent unit derived from α-olefin contained in the copolymer (b-1) is preferably 3 mol % or more and 50 mol % or less, more preferably 5 mol % or more and 40 mol % or less.

The ethylene/α-olefin copolymer (b-1) may also contain unsaturated monomers other than ethylene and α-olefin (hereinafter referred to as “other unsaturated monomers (1)” within the scope of not impairing the effects of the present invention. )”) derived constituent units. Examples of other unsaturated monomers (1) include conjugated polyenes such as butadiene and isoprene; 1,4-hexadiene, 1,7-octadiene, and dicyclopentadiene. , 5-ethylidene-2-nor alkene, 5-vinyl-2-nor alkene, 5-methylene-2-nor alkene, 2,5-nor alkadiene and other non-conjugated polyolefins alkenes.

Among the ethylene/α-olefin copolymers (b-1), ethylene/propylene copolymers, ethylene/butene copolymers, and ethylene/1-octene copolymers are preferred. The propylene/α-olefin copolymer which can be the propylene-based polymer (b-2) includes a structural unit derived from propylene and a structural unit derived from an α-olefin. As the α-olefin, ethylene and an α-olefin having 4 or more carbon atoms are preferred, and ethylene is more preferred. As the α-olefin having 4 to 50 carbon atoms, for example, other than propylene, the same α-olefins as those exemplified as the α-olefin having 3 to 50 carbon atoms serving as the constituent unit of the ethylene/α-olefin copolymer (b-1) can be mentioned. Alpha-olefins.

The constituent unit derived from propylene contained in the propylene-based polymer (b-2) is preferably more than 80 mol % and 100 mol % or less, more preferably 90 mol % or more and 100 mol % or less, and more Preferably more than 95 mol% and less than 100 mol%. In addition, the constituent unit derived from ethylene or α-olefin having 4 or more carbon atoms that may be contained in the propylene-based polymer (b-2) is preferably 0 mol % or more and less than 20 mol %, more preferably 0 mol % or more. It is more than 0 mol % and less than 10 mol %, and more preferably more than 0 mol % and less than 5 mol %.

The propylene-based polymer (b-2) may also contain unsaturated monomers other than propylene, ethylene, and α-olefins having 4 or more carbon atoms (hereinafter referred to as "other unsaturated monomers") within the range that does not impair the effects of the present invention Monomer (2)") derived structural unit.

As the other unsaturated monomer (2), for example, the same conjugated dienes and non-conjugated dienes as the other unsaturated monomer (1) which can become the structural unit of the ethylene/α-olefin copolymer (b-1) may be mentioned. Polyenes.

Among the propylene-based polymers (b-2), a propylene homopolymer and a propylene/ethylene copolymer are preferred. The polyolefin resin (b) can be obtained by polymerizing a monomer corresponding to the constituent unit of the obtained polymer in the presence of a known solid Ti catalyst or a metallocene catalyst or the like commonly used in the production of polyolefin resins . Examples of the metallocene catalyst include metallocene compounds containing rac-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, methyl A catalyst for organoaluminum oxy compounds such as alumoxane and organoaluminum compounds such as triisobutylaluminum. As a more specific manufacturing method of a polyolefin resin (b), the method described in the specification of International Patent Publication No. 2004/87775, etc. are mentioned, for example.

The modified polyolefin resin particle (B) is a particle of a modified polyolefin resin obtained by graft-modifying the above-mentioned polyolefin resin (b) with a polar group-containing monomer. Since the adhesive of the present invention contains modified polyolefin resin particles obtained by graft modification of the polar group-containing monomer, the adhesive force to the substrate made of metal or resin is improved.

As said polar group, the group which has an active hydrogen is mentioned, for example, Specifically, a hydroxyl group, an amine group, a carboxyl group, an acid anhydride group, an ester group, a thiol group, etc. are mentioned. The polar group-containing monomer may have one kind of polar group, or may have two or more kinds of polar groups. In addition, the number of polar groups may be one, or two or more.

As the polar group-containing monomer, the adhesive layer obtained from the adhesive of the present invention can be used to improve the affinity between the adhesive layer obtained from the adhesive of the present invention and the substrate (such as metal, resin) and other adherends, and to further improve the adhesion strength between the adhesive layer and the adherend. From a viewpoint, the monomer which has an acid anhydride group or a carboxyl group is preferable.

Examples of the polar group-containing monomers include hydroxyl group-containing ethylenically unsaturated compounds, amine group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and their anhydrides, vinyl groups Ester compounds, vinyl chloride, thiol group-containing ethylenically unsaturated compounds, other ethylenically unsaturated compounds, aromatic vinyls, and derivatives thereof.

Examples of hydroxyl-containing ethylenically unsaturated compounds include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxyl -3-phenoxy-propyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, glycerol mono(meth)acrylate, pentaerythritol mono(meth)acrylate, Trimethylolpropane mono(meth)acrylate, tetramethylolethane mono(meth)acrylate, butanediol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, Hydroxy-containing (meth)acrylates such as 2-(6-hydrohexyl)ethyl acrylate; 10-dodecen-1-ol, 1-octen-3-ol, 2-methanol noralkene , hydroxystyrene, N-methylol acrylamide, 2-(meth)acryloyloxyethyl acid phosphate, glycerol monoallyl ether, allyl alcohol, allyloxyethanol, 2 -Butene-1,4-diol, glycerol monool, etc. In addition, (meth)acrylate means acrylate and methacrylate, (meth)acrylate means acrylate and methoxyacrylate, (meth)acryloyl means acryl and methacrylate Acrylic base.

As an amine group-containing ethylenically unsaturated compound, the vinylic monomer which has at least 1 type of amine group represented by the following formula or a substituted amine group is mentioned, for example. -NR ¹ R ² In the above formula, R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an alkyl group with 8 to 12 carbon atoms, The cycloalkyl group of 6-9 is preferred. Moreover, as said R< ² >, the group which a part of the said alkyl group and a cycloalkyl group was substituted with a substituent, for example is mentioned.

Examples of such an amino group-containing ethylenically unsaturated compound include aminomethyl (meth)acrylate, propylaminoethyl (meth)acrylate, dimethylaminoethyl methacrylate, ( Alkyl ester compounds of acrylic acid or methacrylic acid such as aminopropyl methacrylate, phenylaminomethyl methacrylate, cyclohexylaminoethyl methacrylate, etc.; N-vinyldiethylamine , N-acetyl vinyl amine and other vinyl amine compounds; acryl amine, methacryl amine, N-methacryl amine, N-methyl methacryl amide, N,N-diamide Methacrylamide, N,N-Dimethylmethacrylamide, N,N-Dimethylaminopropylacrylamide, N,N-Dimethylaminopropylmethacrylamide Acrylamide-based compounds or methacrylamido-based compounds, etc.; imide-based compounds such as p-aminohexyl succinic imide, 2-aminoethyl succinic imide, etc.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one or more polymerizable unsaturated bond groups and epoxy groups in one molecule is used. Examples of such epoxy-containing ethylenically unsaturated compounds include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; unsaturated dicarboxylic acids (e.g. maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, terminal-cis-bicyclo[2,2,1]hept-5-ene- 2,3-dicarboxylic acid (Nadic acid (registered trademark)), terminal-cis-bicyclo[2,2,1]hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl Kinadic acid (registered trademark)) monoglycidyl ester (in the case of monoglycidyl ester, the carbon number of the alkyl group is 1~12), the alkyl glycidyl ester of p-styrene carboxylic acid , Allyl glycidyl ether, 2-methallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-ring Oxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy base-1-hexene, vinylcyclohexene monooxide.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, methacrylic acid, and noralkene. Dicarboxylic acid, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid.

As unsaturated carboxylic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo[2,21]hept-2-ene-5,6-dicarboxylic anhydride are mentioned, for example.

Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl hexanoate, and vinyl tertiary carbonate (Versatic acid). , vinyl laurate, vinyl stearate, vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate.

Examples of the thiol group-containing ethylenically unsaturated compound include allyl mercaptan, 2-vinylbenzyl mercaptan, 3-vinylbenzyl mercaptan, 4-vinylbenzyl mercaptan, vinyl mercaptan Thiophenol derivatives such as thiophenol.

Examples of other ethylenically unsaturated compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate Butyl, 3-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate (meth)acrylates such as cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate.

Examples of the aromatic vinyls include styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene. Examples of derivatives of the above-mentioned compounds include unsaturated carboxylic acid derivatives other than unsaturated carboxylic acid anhydrides. Examples of unsaturated carboxylic acid derivatives include maleic chloride, maleimide, dimethyl maleate, monomethyl maleate, and dimaleic acid. ethyl ester, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo[2,2,1]hept-2-ene-5, Dimethyl 6-dicarboxylate.

The polar group-containing monomers are preferably unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, more preferably unsaturated carboxylic acid anhydrides, from the viewpoint of further enhancing the adhesion strength to substrates such as metals and resins, and more preferably unsaturated carboxylic acid anhydrides. More preferred is maleic anhydride.

These polar group-containing monomers may be used alone or in plural. The modified polyolefin resin particles (B) preferably contain 0.1 to 15 mass % of the constituent units derived from the polar group-containing monomer, more 0.2-10 mass % is preferable, and 0.5-5 mass % is more preferable.

The content ratio (modified amount) of these polar group-containing monomers can be determined, for example, by filling the raw material unmodified polyolefin-based resin with the polar group-containing monomers in the presence of a radical initiator or the like. The loading ratio is adjusted.

In addition, the said modified amount can be calculated|required by well-known means, such as ¹ H-NMR measurement. As specific NMR measurement conditions, the following conditions can be exemplified. In the case of ¹ H-NMR measurement, an ECX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used, the solvent was deuterated o-dichlorobenzene, the sample concentration was 20 mg/0.6 mL, the measurement temperature was 120° C., and the nuclear ¹ H ( 400MHz), the sequence is a single pulse, the pulse width is 5.12μsec (45∘ pulse), the repetition time is 7.0sec, and the accumulation times are set to 500 times or more. The chemical shift of the reference is 0 ppm for the hydrogen of tetramethylsilane. For example, the same result can be obtained by setting the peak of the residual hydrogen from deuterated ortho-dichlorobenzene to 7.10 ppm as the reference value of the chemical shift. The peaks derived from ¹ H or the like of the functional group-containing compound can be assigned according to a conventional method.

In addition, when the monomer having an acidic functional group such as the unsaturated carboxylic acid and its anhydride is used as the polar group-containing monomer, the standard amount of the functional group introduced into the modified olefin polymer may be, for example, Use acid value. Here, as a measuring method of an acid value, the following are mentioned, for example.

(Determination of acid value) The basic operating system is based on JIS K-2501-2003. About 10 g of the modified polyolefin resin particles (B) were accurately weighed and put into a 200 mL high beaker. To this, 150 mL of a mixed solvent obtained by mixing xylene and dimethylformamide at 1:1 (volume ratio) was added as a titration solvent. Several drops of a 1 w/v% phenolphthalein ethanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) were added as an indicator, and the liquid temperature was heated to 80° C. to dissolve the sample. After fixing the liquid temperature at 80°C, titration was performed using a 0.1 mol/L potassium hydroxide solution in 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the acid value was obtained from the titration amount.

The calculation formula is Acid value (mgKOH/g)=(EP1-BL1)×FA×C1/SIZE.

Here, in the above calculation formula, EP1 is the titration amount (mL), BL1 is the blank value (mL), FA is the concentration coefficient of the titration solution (1.00), and C1 is the concentration conversion value (5.611mg/mL: 0.1mol/L KOH 1mL of potassium hydroxide equivalent), SIZE is the sample collection amount (g).

This measurement was repeated three times, and the average value was taken as the acid value. The acid value of the modified polyolefin resin particles (B) is preferably 0.1-100 mgKOH/g, more preferably 0.5-60 mgKOH/g, and particularly preferably 0.5-30 mgKOH/g.

In addition, when maleic anhydride is used as the polar group-containing monomer, an infrared spectrophotometer can also be used, and the amount of grafting can be obtained from the absorption of the carbonyl group of maleic anhydride detected around 1790 cm ⁻¹ .

As a method of graft-copolymerizing a polar group-containing monomer with respect to a polyolefin resin, various methods are mentioned, for example. As such a method, for example, a method of dissolving a polyolefin resin in an organic solvent, adding the above-mentioned polar group-containing monomer and a radical polymerization initiator, heating and stirring to perform a graft copolymerization reaction; The method of heating and melting olefin resin, adding polar group-containing monomer and radical polymerization initiator to the obtained melt, and stirring to make it graft copolymerization; The starting agent is mixed, the obtained mixture is supplied to the extruder, and the method of graft copolymerization reaction is carried out while heating and kneading; for the polyolefin resin, the polar group-containing monomer and the radical polymerization initiator are dissolved in After impregnating the solution in an organic solvent, heating to the highest temperature at which the polyolefin resin does not dissolve, and a method of performing a graft copolymerization reaction, etc.

The reaction temperature is preferably in the range of 50°C or higher, particularly in the range of 80 to 200°C, and the reaction time is about 1 minute to 10 hours. The reaction method may be either a fractional method or a continuous method. In order to uniformly carry out the graft copolymerization, a fractional method is preferred.

The radical polymerization initiator used is not limited as long as it promotes the reaction between the olefin polymer and the polar group-containing monomer, and is particularly preferably an organic peroxide or an organic peroxyester.

Examples of the radical polymerization initiator include benzyl peroxide, dichlorobenzyl peroxide, diisophenylpropyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl peroxide. -2,5-bis(benzoperoxybenzoate)hexyn-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauryl peroxide, tert-butylperoxy Acetate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy) oxide) hexane, tertiary butyl benzoate, tertiary butyl phenyl peroxyacetate, tertiary butyl peroxy isobutyrate, tertiary butyl peroxy second octanoate, tertiary butyl peroxy isobutyrate Organic peroxides such as butyl peroxytrimethyl acetate, cumyl peroxytrimethyl acetate and diethyl tert-butyl peroxyacetate; azobis-isobutyronitrile, bis Azo compounds such as methylazoisobutyronitrile.

Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne are preferable -3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,4-bis(tert-butylperoxyisopropyl)benzene, etc. dialkyl peroxide.

The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by weight relative to 100 parts by weight of the unmodified raw polyolefin resin. The volume-based cumulative 50% particle size (D50) of the modified polyolefin resin particles (B) is preferably 1-1000 μm, more preferably 3-100 μm, and still more preferably 5-30 μm. When D50 of the modified polyolefin resin particle (B) is in the above-mentioned range, good adhesiveness can be imparted to the adhesive of the present invention.

Moreover, the ratio (D90/D50) of the cumulative 90% particle diameter (D90) of the modified polyolefin resin particles (B) based on the volume relative to the D50 of the modified polyolefin resin particles (B) is preferably 1.1 to 4.0 , 1.1~3.5 is better, and 1.1~3.0 is better. When the said ratio (D90/D50) is the said range, favorable adhesiveness can be provided to the adhesive agent of this invention.

The specific gravity of the modified polyolefin resin particles (B) is not particularly limited, but is usually 0.70 to 1.00, preferably 0.80 to 1.00, more preferably 0.85 to 0.95.

The melting point (Tm) of the modified polyolefin resin particles (B) is preferably 95 to 180°C, more preferably 100 to 170°C, and still more preferably 100 to 160°C. By making melting|fusing point into the said range, the adhesive agent which has high adhesive strength can be obtained.

In the present invention, Tm is determined by differential scanning calorimetry (DSC measurement) in accordance with JIS K7122. Specifically, after raising the temperature from 30°C to 200°C at 10°C/min, the temperature was maintained for 3 minutes, then the temperature was lowered to 0°C at 10°C/min, the temperature was maintained for 3 minutes, and then the temperature was maintained at 10°C again. In the process of raising the temperature to 200°C per minute, it was obtained according to JIS K7122 from the thermal pattern at the time of the second heating.

The weight average molecular weight (Mw) of the modified polyolefin resin particles (B) measured by gel permeation chromatography (GPC) in terms of standard polystyrene is preferably, for example, 10,000 or more and 1,000,000 or less, and the molecular weight distribution is (dispersion degree), 1 or more and 3 or less are preferable. Furthermore, the molecular weight distribution is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In the present invention, Mw and Mw/Mn can be specifically measured according to the methods described in the following Examples.

The modified polyolefin resin particles (B) may be used alone or in combination of two or more. In the adhesive of the present invention, the solid weight ratio (A/B) of the thermoplastic adhesive (A) and the modified polyolefin resin particles (B) is preferably 80/20~5/95, more preferably 70/ 30~10/90, and even better 60/40~10/90. When the solid content weight ratio (A/B) is within the above range, the water repellency and adhesiveness of the adhesive of the present invention are particularly good.

Examples of the organic solvent contained in the adhesive of the present invention include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, and decane, and cyclohexane, cyclohexane, and the like. Alicyclic hydrocarbons such as alkene, methylcyclohexane, ethylcyclohexane, decalin, etc., alcohols such as methanol, ethanol, isopropanol, butanol, amyl alcohol, hexanol, propylene glycol, phenol, etc.; acetone, Ketone-based solvents such as methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, acetophenone, etc., and celusu-like solvents such as methyl celusu and ethyl celusu , esters of methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, etc., halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, etc., n-alkane-based solvents, iso-alkane-based solvents solvent, etc. As the above-mentioned organic solvent, from the viewpoints of cost, water repellency performance, and the like, two or more kinds selected from the group consisting of methylcyclohexane, methyl ethyl ketone, ethyl acetate, n-propyl acetate, and toluene are preferred. mixed solvent. Specific examples include n-propyl acetate/methylcyclohexane mixed solution, methylcyclohexane/ethyl acetate mixed solution, methylcyclohexane/methyl ethyl ketone mixed solution, toluene/methyl ethyl ketone Mixed solution, toluene/ethyl acetate mixed solution, etc.

In the adhesive of the present invention, the content of the above-mentioned organic solvent is preferably 50%-95%, more preferably 60%-95%, and more preferably 70%-95% by mass.

The adhesive of the present invention may further contain hydrophobic inorganic particles. The hydrophobic inorganic fine particles have the function of further improving the non-adhesion of the adhesive of the present invention. The hydrophobic inorganic fine particles are preferably a hydrophobic substance having a surface energy of 20 mN/m or more, and the material thereof is not particularly limited. Specific examples of hydrophobic inorganic fine particles include hydrophobic silica, alumina, calcium oxide, calcium carbonate, calcium sulfate, calcium silicate, and the like. Among them, hydrophobic silica or alumina is preferred from the viewpoints of hydrophobicity, cost, and availability from the ultrafine particle material market. In the case of using hydrophobic silica, it may be dry silica or wet silica, but wet silica is relatively advantageous in terms of anti-adhesion properties.

The average particle diameter of the hydrophobic inorganic fine particles is preferably in the range of 1 to 5,000 nm. Ultrafine particles with an average particle diameter of less than 1 nm are difficult to obtain in the market, and are also disadvantageous in terms of cost. When the average particle diameter exceeds 5,000, there is a possibility that the heat-sealability may be hindered, and the effect of preventing adhesion may be reduced. The best ones are hydrophobic wet silica particles with an average particle size of 500~5000nm.

When the adhesive of the present invention contains hydrophobic inorganic particles, the content of the hydrophobic inorganic particle component relative to the thermoplastic resin binder (A) component is preferably 10% to 50%, more preferably 20 to 50% by mass ratio. %, and better 20~40%.

The adhesive agent of the present invention may contain components other than the above-mentioned components that are usually contained in adhesive agents within the range that the object of the present invention can be achieved. In the adhesive of the present invention, the water contact angle of the dry coating film formed by the adhesive is preferably 110∘ or more, more preferably 120∘ or more. When the above-mentioned water contact angle of the adhesive of the present invention is 110∘ or more, the water repellency is excellent. The coating amount of the adhesive at the time of forming the above-mentioned dry coating film is not particularly limited, and can be, for example, 4±0.5 g/cm ² . The measurement method of the water contact angle will be described in detail in the following examples.

The adhesive of the present invention is characterized by high water repellency and high adhesion to metals or resins. In particular, the adhesive of the present invention has high adhesiveness to aluminum foil, polypropylene, and the like.

The adhesive of the present invention can be produced by mixing the thermoplastic resin binder (A), the modified polyolefin resin particles (B), an organic solvent, and optionally used components. When producing the adhesive of the present invention, a thermoplastic resin adhesive composition can also be prepared by mixing the thermoplastic resin adhesive (A) with the above-mentioned organic solvent, and the modified polyolefin resin particles (B) can be mixed with the above-mentioned organic solvent. The solvent is mixed to prepare a modified polyolefin resin particle composition, and the thermoplastic resin binder composition and the modified polyolefin resin particle composition are mixed and produced. [laminated body] A laminate can be obtained from the above-mentioned adhesive. The above-mentioned laminated body includes, for example, a base material and an adhesive layer laminated on at least one surface of the above-mentioned base material, and the above-mentioned adhesive layer is a layer obtained from the above-mentioned adhesive.

As the above-mentioned substrate, for example, resin, metal, plastic substrate metal foil with metal vapor-deposited film, paper, non-woven fabric, among these, resin or metal is preferable. Examples of the above-mentioned resins include polyethylene terephthalate, polyethylene, polypropylene, polyamide, polycarbonate, polyvinyl chloride, cellulose acetate, selevan, and the like, and examples of the above-mentioned metals include aluminum foil. Wait.

The thickness of the base material is not particularly limited, and is usually 25 μm to 300 μm. The said adhesive agent layer is a layer obtained from the said adhesive agent. The method of forming the adhesive layer includes, for example, a method of applying the above-mentioned adhesive on a substrate to form a coating film, and removing volatile components such as an organic solvent contained in the coating film as necessary; and immersing the substrate in the above-mentioned adhesive and taking out A method of removing volatile matter, such as an organic solvent, etc. from the coating film formed of an adhesive which adheres to a base material as needed.

The coating method is not particularly limited, and examples thereof include die coating, flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, contact reverse coating, and microgravure coating. Coating method, roll coating method, blade coating method, rod coating method, roll coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, contact roll coating method , curtain coating method, printing method, etc.

As a method of removing volatile matter from the coating film provided on the above-mentioned base material (drying the coating film), for example, a method of leaving the base material with the coating film at normal temperature (about 20° C.) and normal pressure; The method of pressing and placing the substrate with the coating film to remove the volatile matter contained in the coating film; the method of heating the substrate with the coating film. This heating may be carried out in one stage, or may be carried out in two or more stages.

As a condition of this heating, it is preferable to carry out below the melting|fusing point of the modified polyolefin resin particle (B). When the coating film is heated to a temperature exceeding the melting point of the modified polyolefin resin particles (B), the shape of the modified polyolefin resin particles (B) may be disintegrated, and the contact angle may be lowered. The heating temperature is, for example, 220°C or lower, preferably 200°C or lower, such as 40°C or higher, and the heating time is, for example, 3 seconds or longer, preferably 1 minute or longer, and, for example, 1 hour or shorter.

The thickness of the adhesive layer may be appropriately set depending on the intended application, for example, 0.2 μm or more, preferably 1 μm or more, and, for example, 100 μm or less, preferably 20 μm or less.

The adhesive layer obtained from the adhesive of the present invention can be suitably used as a heat-sealing adhesive layer which can be melted by heat. The adhesive layer is laminated on at least one surface of the above-mentioned substrate. That is, the adhesive layer may be formed only on one side of the base material, or may be formed on both sides of the base material, respectively. Specifically, the laminated body of the present invention can adopt: a substrate composed of an adhesive layer/resin, a substrate composed of an adhesive layer/metal, a substrate composed of an adhesive layer/resin/adhesive layer, and The structure of the substrate composed of the adhesive layer/metal/adhesive layer. In addition, the adhesive agent layer may exist on the whole surface of a base material, and may exist on a part.

As described above, the adhesive of the present invention has high adhesiveness to metals, resins, etc., so in the laminate of the present invention, the adhesive force between the adhesive layer and the substrate is high. In addition, since the adhesive of the present invention has high water repellency as described above, the laminate system of the present invention has high water repellency in the adhesive layer. [Packaging Materials] From the above-mentioned laminate, a packaging material containing the above-mentioned laminate can be obtained. As described above, the above-mentioned lamination system has high adhesive force between the adhesive layer and the base material, and since the adhesive layer has high water repellency, the above-mentioned packaging material can be used in various applications. Specifically, it can be suitably used for food container lids, pharmaceutical containers, cosmetic containers, and the like, and is particularly suitable for food container lids. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these embodiments. 1. Resin properties The physical properties of the resins produced in the following production examples were measured as follows.

<The content ratio of the structural unit derived from a monomer> The content ratio of the structural unit derived from each monomer in the resin obtained in the following production example was calculated|required by ¹³ C-NMR.

<Measurement of melting point and heat of fusion> Using a differential scanning calorimeter (manufactured by TA Instruments; DSC-Q1000), the melting point and the heat of fusion were determined. After heating up from 30°C to 200°C at 10°C/min, hold at 200°C for 3 minutes, cool down to 0°C at 10°C/min, and in the process of raising the temperature to 200°C at 10°C/min again, from the second time For the heat chart at the time of heating, the melting point and the heat of fusion were obtained according to JIS K 7122.

<Measurement of the modified amount of the polar group-containing monomer (content of the structural unit derived from the polar group-containing monomer)> The modified amount was determined by the measurement of ¹ H-NMR. The specific method is as described above.

<Measurement of weight average molecular weight (Mw)> Using a gel permeation chromatograph (manufactured by Shimadzu Corporation; LC-10 series), the weight average molecular weight (Mw) was measured under the following conditions.

‧Detector: Shimadzu Corporation; C-R4A ‧Column: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (manufactured by Tosoh Corporation) ‧Mobile phase: tetrahydrofuran ‧Temperature: 40℃ ‧Flow rate: 0.8ml/min Mw was calculated using a standard curve made of monodisperse standard polystyrene.

2. Resin synthesis Production Example 1-1: Synthesis of thermoplastic resin (a) A 2-liter autoclave fully substituted with nitrogen was charged with 900 ml of hexane, 90 g of 1-butene, and 1 ml of triisobutylaluminum was added. After the temperature was raised to 70°C, propylene was supplied to make the total pressure 7kg/cm ² G, and 0.30 mmol of methylaluminoxane, 0.001 mmol of rac-dimethylsilicon in terms of Zr atom was added. The oxy-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride was polymerized for 30 minutes while continuously supplying propylene to keep the total pressure at 7 kg/cm ² G. After the polymerization, degassing was carried out, the polymer was recovered in a large amount of methanol, and the polymer was dried under reduced pressure at 110° C. for 12 hours. The obtained propylene/1-butene copolymer (thermoplastic resin (a)) had a melting point of 78.3° C., a heat of fusion of 29.2 J/g, a Mw of 330,000, and a propylene content of 67.2 mol %.

Production Example 2-1: Synthesis of Modified Thermoplastic Resin Binder (a1) 3 kg of the above-mentioned propylene/1-butene copolymer (thermoplastic resin (a)) was added to 10 L of toluene, and the temperature was raised to 145° C. under a nitrogen atmosphere to dissolve the copolymer in toluene. Furthermore, 382 g of maleic anhydride and 175 g of di-tertiary butyl peroxide were supplied to the system over 4 hours with stirring, followed by stirring at 145° C. for 2 hours. After cooling, a large amount of acetone was put in to precipitate the modified copolymer, filtered, washed with acetone, and then vacuum-dried.

The obtained maleic anhydride-modified propylene/1-butene copolymer (thermoplastic resin binder (a1)) had a melting point of 75.8° C., a heat of fusion of 28.6 J/g, and a Mw of 110,000. The modified mass (content of the constituent unit derived from maleic anhydride) was 1 mass %.

Production Example 2-2: Synthesis of Modified Thermoplastic Resin Binder (a2) 3 kg of KRATON G1652M (SEBS, manufactured by Kraton Corporation) was added to 10 L of toluene, and the temperature was raised to 145° C. under a nitrogen atmosphere to dissolve the copolymer in toluene. Furthermore, 382 g of maleic anhydride and 175 g of di-tertiary butyl peroxide were supplied to the system over 4 hours with stirring, followed by stirring at 145° C. for 2 hours. After cooling, a large amount of acetone was put in to precipitate the modified copolymer, filtered, washed with acetone, and then vacuum-dried.

The melting point and fusion heat of the obtained maleic anhydride-modified SEBS (modified thermoplastic resin binder (a2)) were not observed, and Mw was 100,000. The modified amount of maleic anhydride in the modified thermoplastic resin binder (a2) (content of the constituent unit derived from maleic anhydride) was 2 mass %.

Production Example 2-3: Synthesis of Modified Polyolefin Resin (b1) In an autoclave with an internal volume of 1.5 L equipped with a stirrer, 100 parts by mass of a propylene/ethylene copolymer with a propylene unit of 99.25 mol % and an ethylene unit of 0.75 mol % and 435 mass parts of toluene were added, and the temperature was raised to 140° C. under stirring. The propylene/ethylene copolymer was completely dissolved in toluene. This solution was kept at 140° C., and 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were simultaneously dropped over 4 hours with stirring. After completion of the dropping, the mixture was further stirred at 140° C. for 1 hour, and a post-reaction was performed to obtain a solution containing a modified polyolefin-based resin (b1). Next, the solution containing the modified polyolefin resin (b1) was cooled to room temperature, and the modified polyolefin resin (b1) was precipitated by adding acetone to the solution. The deposited modified polyolefin resin (b1) was repeatedly washed with acetone, and then dried to recover the modified polyolefin resin (b1). The melting point of the modified polyolefin resin (b1) was 157°C, the modified mass of maleic anhydride (content of the structural unit derived from maleic anhydride) was 1.1 mass %, and Mw was 90,000.

Production Example 2-4: Synthesis of Modified Polyolefin-Based Resin (b2) Except that 100 parts by mass of a propylene/ethylene copolymer containing 99.25 mol% of propylene units and 0.75 mol% of ethylene units was changed to 100 parts by mass of a propylene/ethylene copolymer containing 96.5 mol% of propylene units and 3.5 mol% of ethylene units, and A modified polyolefin-based resin (b2) was obtained in the same manner as in Production Example 2-3 except that 16 parts by mass of maleic anhydride was changed to 30 parts by mass. The melting point of the modified polyolefin-based resin (b2) was 141° C., the modified mass of maleic anhydride (content of the structural unit derived from maleic anhydride) was 2.1 mass %, and Mw was 95,000.

Production Example 2-5: Synthesis of Modified Polyolefin-Based Resin (b3) In an autoclave with an inner volume of 1.5 L equipped with a stirrer, 100 parts by mass of an ethylene/1-octene copolymer with 78 mol% ethylene units and 22 mol% 1-octene units, and 435 parts by mass of toluene were added. The temperature was raised to 140° C. with stirring to completely dissolve the ethylene/1-octene copolymer in toluene to obtain a toluene solution of the ethylene/1-octene copolymer. This solution was kept at 140° C., and 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were simultaneously dropped over 4 hours with stirring. After completion of the dropping, the mixture was further stirred at 140° C. for 1 hour, and a post-reaction was performed to obtain a solution containing a modified polyolefin-based resin (b3). Next, the solution containing the modified polyolefin-based resin (b3) was cooled to room temperature, and the modified polyolefin-based resin (b3) was precipitated by adding acetone to the solution. The deposited modified polyolefin-based resin (b3) was repeatedly washed with acetone, and then dried to recover the modified polyolefin-based resin (b3). The melting point of the modified polyolefin-based resin (b3) was 105° C., the modified mass of maleic anhydride (content of the structural unit derived from maleic anhydride) was 0.9 mass %, and Mw was 100,000.

Production Example 3-1: Synthesis of Thermoplastic Binder Resin Composition (A-1) In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 189 g of KRATON G1652M (SEBS), 94.5 g of methylcyclohexane, and 378 g of n-propyl acetate were charged, and the temperature was heated while flushing with nitrogen. to 95°C. After homogeneously dissolving, a monomer solution in which 94.7 g of methyl methacrylate, 20.6 g of n-butyl acrylate, 66.2 g of styrene, 7.6 g of methacrylic acid, 3.8 g of PERBUTYL O, and 302.4 g of n-propyl acetate will be uniformly mixed for a period of time. The feed was carried out for 2 hours. 60 minutes after the end of the feed, PERBUTYL O 3.0 g was equally divided and added 4 times at 60 minute intervals. After PERBUTYL O was added four times, it was left to react for 3 hours, and then 340.2 g of n-propyl acetate was added to dilute to 25% non-volatile content to obtain a thermoplastic binder resin composition (A-1).

Production Example 3-2: Synthesis of Thermoplastic Binder Resin Composition (A-2) 100 g of the modified thermoplastic binder resin (a1) was heated and dissolved in 400 g of a mixed solvent of methylcyclohexane/ethyl acetate=80/20 to prepare a thermoplastic binder resin composition (A-2).

Production Example 3-3: Synthesis of Thermoplastic Binder Resin Composition (A-3) 100 g of the modified thermoplastic binder resin (a2) was heated and dissolved in 400 g of a mixed solvent of methylcyclohexane/ethyl acetate=60/40 to prepare a thermoplastic binder resin composition (A-3).

Production Example 3-4: Synthesis of Modified Polyolefin Particle Composition (B-1) In an autoclave with a stirrer, 5.5 g of the modified polyolefin-based resin (b1) obtained in Production Example 2-3, 12.5 g of the modified polyolefin-based resin (b2) obtained in Production Example 2-4, and toluene/methyl ethyl acetate were added. Base ketone=78/22 mixed solvent 82g, heated to 130°C to completely dissolve the thermoplastic resin. Then, it cooled slowly with stirring, and obtained the modified polyolefin particle composition (B-1) in which 18 mass % of nonvolatile content (solid content) was uniform and milky white, and the modified polyolefin resin particle was dispersed in a solvent. The obtained modified polyolefin particle composition (B-1) had a particle diameter D50 of 10.1 μm, a particle diameter D90 of 27.3 μm, and D90/D50 of 2.73.

Production Example 3-5: Synthesis of Modified Polyolefin Particle Composition (B-2) In an autoclave with a stirrer, 15 g of the modified polyolefin-based resin (b3) obtained in Production Example 2-5 and 85 g of a mixed solvent of toluene/ethyl acetate (mass ratio 55/45) were added, and heated to 130° C. to modify 15 g of the polyolefin-based resin (b3) was completely dissolved. Then, it cooled slowly with stirring, and obtained the uniform milky white, modified|denatured polyolefin particle composition (E) of 15 mass % of nonvolatile matter (solid content). The obtained modified polyolefin particle composition (B-2) had a particle diameter D50 of 17.7 μm, a particle diameter D90 of 21.1 μm, and D90/D50 of 1.19. 3. Manufacture of adhesive [Examples 1 to 21] Thermoplastic binder resin compositions (A-1) to (A-3) obtained in Production Examples 3-1 to 3-3, and modified polyolefin particles obtained in Production Examples 3-4 and 3-5 Compositions (B-1), (B-2), n-propyl acetate (C), and methylcyclohexane (D) were mixed according to the weight ratio shown in Table 2 to prepare thermoplastic adhesive (A) and modified An adhesive having a solid mass ratio ((A)/(B)) of the polyolefin resin particles (B) of 60/40 to 10/90.

[Comparative Example 1] The thermoplastic adhesive resin composition (A-1) obtained in Production Example 3-1 and n-propyl acetate (C) were mixed at the weight ratio shown in Table 2 to prepare an adhesive.

[Comparative Example 2] The thermoplastic adhesive resin composition (A-3) obtained in Production Example 3-3 and methylcyclohexane (D) were mixed at the weight ratio shown in Table 2 to prepare an adhesive.

[Comparative Example 3] The modified polyolefin particle composition (B-1) obtained in Production Example 3-4 and n-propyl acetate (C) were mixed at the weight ratio shown in Table 2 to prepare an adhesive.

Table 1 shows the organic solvents contained in the thermoplastic binder resin compositions (A-1) to (A-3) and the modified polyolefin particle compositions (B-1) and (B-2). The particle diameters of the modified polyolefin resin particles contained in the modified polyolefin particle compositions (B-1) and (B-2) were measured by the following method. The results are shown in Table 1.

<Particle size measurement> The particle sizes of the modified polyolefin particle compositions (B-1) and (B-2) obtained in Production Example 3-4 and Production Example 3-5 were obtained by filtering the coating material with 100 μ filter paper, and then filtering the residue in sodium chloride. 0.9 g, 100 ml of distilled water, and 140 ml of isopropyl alcohol were ultrasonically dispersed for 2 minutes, and then measured using Multisizer 4 manufactured by Beckman Coulter Co., Ltd. The 50% value of the obtained volume statistics was set as D50, and the 90% value was set as D90. Moreover, the ratio (D90/D50) was calculated|required from the obtained value of D50 and D90.

[Table 1] organic solvent D50 D90 D90/D50 Thermoplastic resin binder composition A-1 nPAc/MCH (91.5/8.5) A-2 MCH/EA(80/20) A-3 MCH/MEK(60/40) Acid-modified polyolefin particle composition B-1 TOL/MEK(78/22) 10.0 27.3 2.70 B-2 TOL/EA(55/45) 17.7 21.1 1.19 Each symbol in Table 1 is abbreviated below. The ratio in parentheses is the mass ratio. nPAc: n-propyl acetate MCH: methylcyclohexane EA: ethyl acetate MEK: methyl ethyl ketone TOL: toluene The properties of the adhesives obtained in the above Examples and Comparative Examples were determined by the following methods. The results are shown in Table 2.

<Measurement of AL/PP Adhesion Strength> The adhesives of Examples 1 to 21 and Comparative Examples 1 to 3 were respectively coated on aluminum foil (AL foil), and dried at 80°C for 30 seconds (dry coating weight 4±0.5 g/m ² ), make a coating film. The coated surface of the aluminum foil was used as the pressure-bonding surface, and the polypropylene (PP) sheet was thermally pressure-bonded at 180° C., 2kgf/cm ² , and 1 second. Then, a size of 15 mm in width was cut out to prepare a test piece. This test piece was subjected to a 180∘ peel test at a crosshead speed of 100 mm/min using a universal tensile measuring device to measure the peel strength of AL/PP.

<Measurement of water contact angle> The adhesives of Examples 1 to 21 and Comparative Examples 1 to 3 were applied to AL foil, respectively, and dried at 80° C. for 30 seconds (dry coating amount 4±0.5 g/m ² ) to prepare a coating. membrane. Using the water contact angle measuring device CA-V made by Kyowa Interface Science Co., Ltd., measure the water contact angle relative to the coating film surface of 1 sample at 3 places, and the average value of these equivalent values is used as the water contact angle of the adhesive. .

<Tape Adhesion Test> The adhesives of Examples 1 to 21 and Comparative Examples 1 to 3 were respectively coated on AL foil, and dried at 80° C. for 30 seconds (dry coating amount 4±0.5 g/m ² ) to prepare a coating. membrane. To the obtained coating film, after attaching the Serovan tape (Nichiban Co., Ltd. product, registered trademark), it was quickly stretched to 90° to peel it off, and the coating film was visually confirmed to be missing, and the adhesiveness of the adhesive was evaluated according to the following criteria. Tightness of the foil.

A: No defect B: slightly missing C: There are many gaps

[Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Comparative Example 1 Comparative Example 2 Comparative Example 3 Adjuvant Thermoplastic Binder Resin Composition A-1 (parts by mass) 31.2 26 20.8 15.6 10.4 5.2 52 A-2 (parts by mass) 35.9 29.1 22.4 15.8 10.4 4.7 A-3 (parts by mass) 35.9 29.1 22.4 15.8 10.4 4.7 35.9 22.4 10.4 65 Modified polyolefin particle composition B-1 (parts by mass) 28.9 36.1 43.3 50.5 57.8 65 26.6 32.3 37.3 40.9 46.1 46.8 26.6 32.3 37.3 40.9 46.1 46.8 72.2 B-2 (parts by mass) 31.9 44.7 55.3 organic solvent C (parts by mass) 39.9 37.9 35.9 33.9 31.8 29.8 48 27.8 D (parts by mass) 37.5 38.6 40.3 43.3 43.5 48.5 37.5 38.6 40.3 43.3 43.5 48.5 32.2 32.9 34.3 35 count 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Solid mass ratio of thermoplastic binder (A) and modified polyolefin resin particles (B) ((A)/(B)) 60/40 50/50 40/60 30/70 20/80 10/90 60/40 50/50 40/60 30/70 20/80 10/90 60/40 50/50 40/60 30/70 20/80 10/90 60/40 40/60 20/80 100/0 100/0 0/100 continuity AL/PP bond strength (g/15mm) 840 1100 1240 1390 1550 1380 1210 1190 1250 1210 1360 1140 1380 1460 1450 1590 1610 1680 1120 1220 1390 900 1600 1050 water repellency Water contact angle (∘) 121 127 137 128 132 >150 122 140 >150 >150 >150 >150 119 126 138 >150 >150 >150 121 137 >150 75 102 >150 AL substrate dense adhesive adhesive tape A A A B B B A A A B B B A A A A A B A A B A A C

Claims (11)

An adhesive contains a thermoplastic resin binder (A), modified polyolefin resin particles (B) and an organic solvent. The adhesive according to claim 1, wherein the water contact angle of the dry coating film of the adhesive is 110∘ or more. The adhesive according to claim 1 or 2, wherein the volume-based cumulative 50% particle size (D50) of the modified polyolefin resin particles (B) is 1 to 1000 μm. The adhesive according to any one of claims 1 to 3, wherein the ratio (D90/D50) of the cumulative 90% particle diameter (D90) to D50 on a volume basis in the modified polyolefin resin particles (B) is 1.1 ~4.0. The adhesive according to any one of claims 1 to 4, wherein the thermoplastic resin binder (A) contains a resin selected from the group consisting of acrylic resins, styrene-based resins, ABS resins, vinyl chloride resins, polyethylene resins, and polypropylene resins. , at least one thermoplastic resin of polybutene resin, polyamide resin, polycarbonate, polyacetal, fluorine resin, silicone resin, polyester resin and modified resin of these. The adhesive according to any one of claims 1 to 5, wherein the solid content mass ratio ((A/B)) of the thermoplastic resin binder (A) and the modified polyolefin resin particles (B) is 80/ 20~5/95. The adhesive according to any one of claims 1 to 6, further comprising hydrophobic inorganic particles. A laminate comprising a base material and an adhesive layer laminated on at least one surface of the base material, wherein the base material is resin or metal, and the adhesive agent layer is the adhesive according to any one of claims 1 to 7 obtained layer. The laminate according to claim 8, wherein the water contact angle of the adhesive layer is 110∘ or more. The laminate according to claim 8 or 9, wherein the adhesive layer is a heat-sealing layer. A packaging material containing the laminate of any one of claims 8 to 10.