JP2014028914A - Hot melt adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot melt adhesive having excellent adhesive strength with a molded article of a polyolefin resin etc. and an adherend having polarity.SOLUTION: A hot melt adhesive contains a copolymer having an acid value of 50 to 250 mgKOH/g, in which polyolefin and unsaturated (poly)carboxylic acid (anhydride) are included as constitutional units. Furthermore, the hot melt adhesive preferably contains an aliphatic unsaturated hydrocarbon added as a constitutional unit of the copolymer. The hot melt adhesive also may contain a tackifier resin.

Description

  The present invention relates to a hot melt adhesive. More specifically, the present invention relates to a hot melt adhesive excellent in adhesiveness between a thermoplastic resin, particularly a polyolefin resin, and another highly polar adherend (for example, polyester, ABS resin, polycarbonate, etc.).

Polyolefin resins (polypropylene, polyethylene, etc.) are extremely useful materials in the industry because they are excellent in cost, processability, light weight, and have advantages such as recyclability. Hot melt adhesives for bonding molded articles made of these polyolefin resins are used particularly for automobile interior materials and the like. However, since polyolefin resins are nonpolar, various devices have been applied to hot-melt adhesives for polyolefin resins.
Conventionally, hot melt adhesives for polyolefin resins include those obtained by adding a liquid plasticizer such as a tackifying resin component and process oil to chloroprene rubber, styrene butadiene styrene block copolymer (SBS), and the like. (For example, refer to Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 3-160083 JP-A-8-60121

However, in the method of adding a liquid plasticizer such as a tackifying resin component and process oil to chloroprene rubber, styrene butadiene styrene block copolymer (SBS), etc., although the adhesion between polyolefin resin molded products is excellent, Since the fluidity, that is, the coating property is inferior, the coexistence of cohesive force and coating property cannot be satisfied. Moreover, the adhesiveness with respect to the molded article of polyolefin resin and a highly polar adherend is inadequate, and improvement was desired.
An object of the present invention is to provide a hot melt adhesive having excellent adhesion to a molded article of polyolefin resin or the like and an adherend having high polarity.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention contains a copolymer (X) having a polyolefin (A) and an unsaturated (poly) carboxylic acid (anhydride) (B) as structural units and an acid value of 50 to 250 mgKOH / g. This is a hot melt adhesive (H).

The hot melt adhesive of the present invention has the following effects.
(1) Since it has moderate fluidity, it is excellent in coatability.
(2) Excellent adhesion between a polyolefin resin molded article and a highly polar adherend.

[Polyolefin (A)]
The polyolefin (A) in the present invention includes one or two or more (co) polymers of olefins, and one or more of olefins and one or more of other monomers. A polymer is included.
Examples of the olefin include alkenes having 2 to 30 carbon atoms (hereinafter abbreviated as C) such as ethylene, propylene, 1- and 2-butene, and isobutene, and C5-30 α-olefins (1-hexene, 1-hexene, Decene, 1-dodecene, etc.); other monomers include C4-30 unsaturated monomers having copolymerizability with olefins, such as vinyl acetate.

Specific examples of (A) include ethylene unit-containing (propylene unit-free) (co) polymers such as high, medium and low density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1- Butene, etc.), C5-30 α-olefin (1-hexene, 1-dodecene, etc.), vinyl acetate, etc. [weight ratio is the coating property of hot melt adhesive (H) and (A) Preferably from 30/70 to 99/1, more preferably from 50/50 to 95/5] from the viewpoint of the amount of double bonds in the molecular ends and / or molecular chains; Co) polymer, for example, polypropylene, copolymer of propylene and C4-30 unsaturated monomer (same as above) (weight ratio is the same as above); ethylene / propylene copolymer [weight ratio is hot melt adhesive( ) And (A) from the viewpoint of the molecular terminal and / or the amount of double bonds in the molecular chain, preferably 0.5 / 99.5 to 30/70, more preferably 2/98 to 20 /. 80]; (co) polymers of C4 or higher olefins such as polybutene.
Among these, polyethylene, polypropylene, ethylene / propylene copolymer are preferable from the viewpoint of copolymerization with an unsaturated (poly) carboxylic acid (anhydride) (B) and an aliphatic unsaturated hydrocarbon (C) described later. Polymers, propylene / C4-30 unsaturated monomer copolymers, more preferably ethylene / propylene copolymers, and propylene / C4-30 unsaturated monomer copolymers.

  Number average molecular weight of (A) [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method described later. same as below. ] Is preferably 800 to 50,000, more preferably 1,000 to 45,000, from the viewpoint of the adhesiveness and productivity of the hot melt adhesive (H).

The measurement conditions of Mn by GPC in the present invention are as follows.
Apparatus: High-temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Corporation]
Detector: Refractive index detector Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Made by Polymer Laboratories, Inc.]
Column temperature: 135 ° C

(A) is a molecular terminal and / or molecule from the viewpoint of copolymerization with an unsaturated (poly) carboxylic acid (anhydride) (B) or (B) and an aliphatic unsaturated hydrocarbon (C) described later. It is preferable to have a double bond in the chain.
The number of double bonds in the molecular end and / or molecular chain per 1,000 carbon atoms (also referred to as 1,000 carbon atoms) of (A) is (A) and (B) or (B) And from the viewpoint of copolymerization with (C) and productivity of the copolymer (X), preferably 0.1 to 20, more preferably 0.3 to 18, and particularly preferably 0.5 to 15 It is.
Here, the number of double bonds can be determined from the spectrum of (A) ¹ H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peak in the spectrum is assigned, and the number of double bonds in (A) and (A) are calculated from the integral value derived from double bonds and the integral value derived from (A) at 4.5 to 6 ppm in (A). Is calculated, and the number of double bonds in the molecular end and / or molecular chain per 1,000 carbon atoms in (A) is calculated. The number of double bonds in the examples described later followed this method.

  The production method of (A) includes polymerization methods (for example, those described in JP-A-59-206409) and degradation methods [thermal, chemical and mechanical degradation methods, etc. Examples of the formation method (hereinafter sometimes referred to as thermal degradation method) include those described in JP-B No. 43-9368, JP-B No. 44-29742, and JP-B No. 6-70094].

  The polymerization method includes a method of (co) polymerizing one or more of the olefins, and a method of copolymerizing one or more of the olefins and one or more of the other monomers. It is.

  In the degradation method, a polyolefin (A0) having a high molecular weight [preferably Mn 30,000 to 400,000, more preferably 50,000 to 200,000] obtained by the polymerization method is thermally, chemically or mechanically used. The method of degrading is included.

Among the degradation methods, in the thermal degradation method, the polyolefin (A0) is continuously introduced for 0.5 to 10 hours at 300 to 450 ° C. in the absence of an organic peroxide under nitrogen aeration. Or a method of thermally degrading discontinuously and (2) a method of thermally degrading continuously or discontinuously at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide. It is.
Among these, it is preferable from the viewpoint of the copolymerizability between (A) and (B) or (B) and (C) obtained that the number of double bonds in the molecular terminal and / or molecular chain is larger. This is the method (1) in which a product is easy to obtain.

  Among these production methods of (A), those having a larger number of double bonds in the molecular end and / or molecular chain are easily obtained, and (A) and (B) or (B) and (C) From the viewpoint of easy copolymerization of these, a degradation method is preferred, and a thermal degradation method is more preferred.

[Unsaturated (poly) carboxylic acid (anhydride) (B)]
The unsaturated (poly) carboxylic acid (anhydride) (B) in the present invention is a C3-30 (poly) carboxylic acid (anhydride) having one polymerizable unsaturated group. In the present invention, the unsaturated (poly) carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic anhydride.
Among these (B), as unsaturated monocarboxylic acid, aliphatic (C3-24, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic ring-containing (C6-24, For example, cyclohexene carboxylic acid); unsaturated poly (2-3 or more) carboxylic acid (anhydride) include unsaturated dicarboxylic acid (anhydride) [aliphatic dicarboxylic acid (anhydride) (C4-24, eg malee Acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof), alicyclic dicarboxylic acids (anhydrides) (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptide) Tendicarboxylic acid, methyltetrahydrophthalic acid, and anhydrides thereof)], unsaturated tricarboxylic acid (anhydride) [aliphatic acid Carboxylic acid (anhydrides) (C5-24, such as aconitic acid, 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid, and anhydrides thereof), alicyclic Containing tricarboxylic acids (anhydrides) (C9-24, such as 4-cyclohexene-1,2,3-tricarboxylic acid, 4-cycloheptene-1,2,3-tricarboxylic acid and anhydrides thereof) and the like. . (B) may be used alone or in combination of two or more.
Of the above (B), an unsaturated dicarboxylic acid (anhydride) is preferable from the viewpoint of copolymerization with the aliphatic unsaturated hydrocarbon (C) described later, and an aliphatic unsaturated dicarboxylic acid (anhydride) is more preferable. Particularly preferred are aliphatic unsaturated carboxylic acid anhydrides, and most preferred is maleic anhydride.

[Aliphatic unsaturated hydrocarbon (C)]
In the aliphatic unsaturated hydrocarbon (C) in the present invention, a C2-30 alkene, a C6 to 36 (more preferably C8 to 30) linear α-olefin and a branched chain constituting the (A) are included. In addition to the α-olefin, C4-30 other unsaturated monomers (butadiene and the like) having copolymerizability with olefin are included.
Examples of the linear α-olefin include 1-hexene, 1-octene, 1-nonene, 1-decene, and a mixture of two or more thereof.
Examples of the α-olefin having a branched chain include propylene trimer, propylene tetramer, and a mixture of two or more thereof.
Among the above (C), from the viewpoint of copolymerization with (A) and (B) and the adhesiveness of the obtained hot melt adhesive, it is preferable to use C6 to 36 (more preferably C8 to 30). A chain α-olefin and a branched chain α-olefin.

[Radical initiator (D)]
In the copolymer (X) in the present invention, the (A), (B), or (A), (B), (C) is a radical generation source [radical initiator (D), heat, light, etc. ] In the presence or absence of].
Examples of the radical initiator (D) include azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile)], peroxides [monofunctional ( (Having one peroxide group in the molecule) (benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.) and polyfunctional (having two or more peroxide groups in the molecule) [2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxyhexahydroterephthalate, diallyl peroxydicarbonate, etc.]] and the like.
Of these, (A), (B), or (A), (B), (C) graft copolymerization viewpoint, that is, to be described later, (A) is a trunk, (B) or (B) From the viewpoint of the formability of the graft copolymer having (C) (co) polymer as a branch, a peroxide is preferable, a monofunctional peroxide is more preferable, and di-t-butyl is particularly preferable. Peroxide, lauroyl peroxide, dicumyl peroxide.

  The use amount of (D) is preferably based on the total weight of (A), (B) or the total weight of (A), (B), (C) from the viewpoint of reactivity and side reaction suppression. 0.05 to 10%, more preferably 0.2 to 5%, particularly preferably 0.5 to 3%.

[Copolymer (X)]
The copolymer (X) in the present invention comprises the polyolefin (A) and the unsaturated (poly) carboxylic acid (anhydride) (B) as structural units.
In addition, (X) is the addition of an aliphatic unsaturated hydrocarbon (C) to the above structural unit from the viewpoint of further improving the adhesiveness of the hot melt adhesive by increasing the copolymerization ratio of (B), and (A ), (B) and (C) may be used as a copolymer.
In the production of (X), styrene or a styrene derivative (thing of C9 to C15, for example, methylstyrene, α-methylstyrene, p-methoxystyrene, m-butylstyrene, etc.) is not included as a structural unit of copolymerization. Is preferable from the viewpoint of the adhesiveness of a molded product (hereinafter sometimes simply referred to as a molded product).

  The content of each component based on the total weight of (A), (B), and (C) is as follows. (A) is the productivity and adhesiveness of a hot melt adhesive comprising the copolymer (X). From the viewpoint of improvement, it is preferably 20 to 85%, more preferably 30 to 80%; (B) is preferably 8 to 45%, more preferably 10 to 40% from the viewpoint of adhesiveness and productivity of the hot melt adhesive. ; (C) is usually 70% or less, preferably from 5 to 65%, more preferably from 10 to 50% from the viewpoint of productivity of hot melt adhesive and improvement of adhesiveness.

  The weight ratio [(A) / (B)] of (A) and (B) in (X) is preferably 30/70 from the viewpoint of the productivity of (X) and the adhesiveness of the hot melt adhesive described later. ~ 92/8, more preferably 35 / 65-80 / 20; (A) to (C) weight ratio [(A) / (C)] is the productivity of (X) and adhesion of hot melt adhesive From the viewpoint of properties, it is preferably 23/77 to 94/6, more preferably 30/70 to 85/15; the weight ratio of (A) to the sum of (B) and (C) [(A) / [( B) + (C)]] is preferably 20/80 to 85/15, more preferably 30/70 to 80/20 from the viewpoint of the productivity of (X) and the adhesiveness of the hot melt adhesive; The weight ratio of (B) to (C) [(B) / (C)] depends on the adhesiveness of the hot melt adhesive and the productivity of (X). From preferably more preferably 11 / 89-90 / 10, 15 / 85-80 / 20.

  Copolymer (X) is prepared in the presence or absence of radical initiator (D) in the presence of polyolefin (A) and unsaturated (poly) carboxylic acid (anhydride) (B), or (A), (B ) And an aliphatic unsaturated hydrocarbon (C).

The specific production method (X) includes the following methods [1] and [2].
[1] (A), (B), or (A), (B), (C) is a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene) Etc.), halogenated hydrocarbons (di-, tri-, and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-n-) Butyl ether, di-t-butyl ether, dioxane, etc.)], and if necessary, (D) [or a solution in which (D) is dissolved in an appropriate organic solvent (the same as above)], which will be described later. A chain transfer agent (t) and a polymerization inhibitor (f), and stirring with heating (solution method);
[2] (A), (B), or (A), (B), (C) and, if necessary, (D), (t), (f) are mixed in advance, an extruder, a Banbury mixer, a kneader A method of melting and kneading using the above (melting method)

  The reaction temperature in the solution method may be a temperature at which (A) is dissolved in an organic solvent, and (A), (B), or (A), (B), (C) copolymerizability and productivity. From this viewpoint, it is preferably 50 to 220 ° C, more preferably 110 to 210 ° C, and particularly preferably 120 to 180 ° C.

  Further, the reaction temperature in the melting method may be a temperature at which (A) melts, and (A), (B) or (A), (B), (C) copolymerizability and reaction product. From the viewpoint of the decomposition temperature, it is preferably 120 to 260 ° C, more preferably 130 to 240 ° C.

Examples of the chain transfer agent (t) include alcohols (C1-24, such as methanol, ethanol, 1-propanol, 2-butanol, allyl alcohol); thiols (C1-24, such as ethanethiol, propanethiol, 1- and 2-butanethiol); aldehydes (C2-18, such as n- and sec-butyraldehyde, 1-pentylaldehyde); phenols (C6-36, such as phenol, o-, m- and p-cresol); amines (C3 To 24, such as diethyl methylamine, triethylamine, diphenylamine); disulfides (C2-24, such as diethyl disulfide, di-1-propyl disulfide).
The amount of (t) used is usually 30% or less based on the total weight of (A) and (B) or the total weight of (A), (B) and (C), (A) and (B) Or from the viewpoint of the copolymerizability of (A), (B) and (C) and the productivity of (X), it is preferably 0.1 to 20%.

Examples of the polymerization inhibitor (f) include catechol (C6-36, such as 2-methyl-2-propylcatechol), quinone (C6-24, such as p-benzoquinone), nitro compound (C3-24, such as nitrobenzene), Stabilized radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6-tetramethyl-1-piperidinyl oxide (TEMPO)].
The amount of (f) used is usually 5% or less based on the total weight of (A) and (B) or the total weight of (A), (B) and (C), productivity, (A), From the viewpoint of the stability of (B) and (C) and the reactivity of (A), (B) and (C), it is preferably 0.01 to 0.5%.

  Mn of (X) is preferably 1,500 to 70,000, more preferably 2,000 to 60,000, particularly preferably 2,500 to 50, from the viewpoint of the adhesiveness and coating properties of the hot melt adhesive. , 000.

The acid value of (X) is preferably 50 to 250 mg KOH / g (only numerical values are shown below), preferably 65 to 200, particularly preferably 80 to 180 from the viewpoint of the adhesiveness and coating properties of the hot melt adhesive. . When the acid value of (X) is less than 50, the adhesive property of the hot melt adhesive is deteriorated, and when it exceeds 250, the coating property of the hot melt adhesive is deteriorated.
The acid value here is a value obtained by measurement according to the following procedures (i) to (iii) according to JIS K0070.
(I) 1 g of (X) is dissolved in 100 g of xylene adjusted to 100 ° C.
(Ii) Titration with 0.1 mol / L potassium hydroxide ethanol solution [trade name “0.1 mol / L ethanolic potassium hydroxide solution”, manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator at the same temperature. I do.
(Iii) The amount of potassium hydroxide required for titration is converted to mg, and the acid value (unit: mgKOH / g) is calculated.
In the above measurement, one acid anhydride group is equivalent to one carboxyl group. The acid value in the examples described later was in accordance with this method.

Examples of the method for bringing the acid value of (X) into the above range include the following methods.
(1) A method in which a constituent unit of (A) and (B) is copolymerized under a condition of being suspended or dissolved in a suitable organic solvent and stirring under heating.
(2) A method in which (C) is further added to the structural unit to (A) and (B) and copolymerized in the same manner as in (1).
The above (1) specifically includes (A) and (B) as a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, decane, dodecane, benzene, toluene, xylene, etc.), Halogenated hydrocarbons (di-, tri- and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, diethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-i-propyl) Ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)], and if necessary, (D) [or (D) in an appropriate organic solvent (same as above). The dissolved solution], the chain transfer agent (t) and the polymerization inhibitor (f) are added and heated and stirred.
Of the above (1) and (2), (2) can easily control the copolymerization rate of (B) by adding (C) to the structural unit, so that the acid value of (X) can be within the above range. This is the preferred method.

Moreover, the following are contained in the form of copolymer (X).
[1] A graft copolymer in which (A) is a trunk and (B) or a (co) polymer of (B) and (C) is a branch.
[2] A random and / or block copolymer of (A) and (B) or (A), (B) and (C).
In the form of [1], (A) and (B) or (A), (B) and (C) are preferably heated and melted in the presence of (D) (more preferably a peroxide), or It can be formed by suspending or dissolving in an organic solvent, adding the chain transfer agent (t) and the polymerization inhibitor (f) if necessary, and stirring with heating.
The form of the above [2] is preferably (A) and (B), or (A), (B) and (C) are heated and melted in the presence of (D) (more preferably an azo compound), or appropriate It can be formed by suspending or dissolving in an organic solvent, and further adding a chain transfer agent (t) and a polymerization inhibitor (f), which will be described later, if necessary, followed by heating and stirring.
Of the forms [1] and [2], the form [1] is preferable from the viewpoint of the adhesiveness of the hot melt adhesive described later.

[Hot melt adhesive (H)]
The hot melt adhesive (H) of the present invention is a copolymer having the polyolefin (A) and the unsaturated (poly) carboxylic acid (anhydride) (B) as structural units and an acid value of 50 to 250 mgKOH / g. (X) is contained.

The hot melt adhesive of the present invention may further contain a tackifier resin (E) if necessary. Examples of (E) include various resins, for example, bonding technology VOL. 20, (2), 13 (2000) can be used.
Examples of (E) include rosin / rosin derivative resins (Mn 200 to 1,000, such as polymerized rosin, rosin ester, phenol-modified products and unsaturated acid-modified products thereof), terpene resins [Mn 300 to 1200, such as α-pinene, (Co) polymers such as β-pinene and limonene and their phenol-modified products], coumarone resin, coumarone-indene resin, petroleum resin [Mn 300 to 1,200, for example, C5 fraction, C9 fraction, C5 / C9 fraction And (co) polymers such as dicyclopentadiene], styrene resins [Mn 500 to 5,000, for example, (co) polymers such as styrene, α-methylstyrene and vinyltoluene, and glass transition point (hereinafter abbreviated as Tg). Of 40 ° C. or higher], xylene resin (Mn 300 to 3,000, for example, xylene formaldehyde resin), One or more selected from enol resins (Mn 300 to 3,000, such as phenol formaldehyde resin, phenol xylene formaldehyde resin), ketone resins (Mn 300 to 3,000, methylcyclohexanone-formaldehyde condensate) and hydrogenated products of these resins These resins are mentioned. Among these, from the viewpoint of adhesion, hydrogenated terpene resin and hydrogenated petroleum resin, more preferably hydrogenated product of (co) polymerized petroleum resin of C9 fraction and C5 / C9 fraction It is.

  Mn of (E) is preferably 200 to 3,000, more preferably 300 to 800 from the viewpoint of adhesion and coating properties, and the ring and ball softening point (based on JIS K6863) is adhesive and coating. From a viewpoint of property, Preferably it is 80-150 degreeC, More preferably, it is 100-140 degreeC.

  The hot melt adhesive of the present invention further includes a colorant (F1), a reinforcing agent (F2), a matting agent (F3), an antistatic agent (F4), and a dispersant as long as the effects of the present invention are not inhibited as necessary. One or more additives selected from the group consisting of (F5), flame retardant (F6), foaming agent (F7), antioxidant (F8), ultraviolet absorber (F9) and plasticizer (F10) (F) can be contained.

The total amount of (F) used in the adhesive of the present invention is usually 30% or less based on the total weight of the adhesive, and preferably 1 to 10% from the functional expression of (F) and an industrial viewpoint. .
The use amount of each additive (F) based on the total weight of the adhesive is as follows: (F1) is usually 10% or less, preferably 1 to 5%; (F2) is usually 15% or less, preferably 3 to 10%. ; (F3) is usually 20% or less, preferably 1 to 10%; (F4) is usually 10% or less, preferably 1 to 5%; (F5) is usually 20% or less, preferably 0 to 15%, especially Preferably 0 to 10%; (F6) is usually 15% or less, preferably 3 to 10%; (F7) is usually 1 to 20% or less, preferably 5 to 15%; (F8) is usually 3% or less, Preferably, it is 0.01 to 1%; (F9) is usually 3% or less, preferably 0.01 to 1%; (F10) is usually 20% or less, preferably 5 to 15%.
When the additive is the same and overlaps between (F1) to (F10), the amount of each additive having the corresponding additive effect is not used regardless of the effect as the other additive. Considering that the effect as an additive can be obtained at the same time, the amount used is adjusted according to the purpose of use.

  Although it does not specifically limit as a manufacturing method of the hot-melt-adhesive of this invention, For example, (1) Copolymer (X) and (E) and (F) which are added as needed are heat-melted (normally 80-250 degreeC). A method of kneading; (2) A method of adding an organic solvent (toluene, xylene, etc.), dissolving each component by heating (usually 60 to 180 ° C.), uniformly mixing, and then distilling off the solvent. In any method, it is preferable to carry out in an inert gas atmosphere such as nitrogen gas in order to prevent resin deterioration. Among the above methods, the method (1) is preferable from the industrial viewpoint. Moreover, a heating melt kneader can be used as the mixing device. Examples of the heat-melt kneader include a mixer having a highly compressible screw or ribbon stirrer, a kneader, a single or multi-screw extruder, and a mixer.

Examples of the polyolefin resin to which the hot melt adhesive of the present invention is applied include those having the same composition as the above (A), and Mn is preferably 30,000 to 400,000, more preferably 50,000 to 300. , 000.
In addition, examples of the adherend having high polarity to be applied include those having a solubility parameter (hereinafter abbreviated as SP value) of 10.0 to 13.0.
Here, the SP value means an amount defined by the following formula when the cohesive energy density is ΔE (unit is cal / mol) and the molecular volume is V (unit is cm ³ / mol). .

SP value = (ΔE / V) ^1/2 [unit is (cal / cm ³ ) ^1/2 ]

For example, the Fedors method is known as a specific method for obtaining the SP value, and this method includes “A Method for Estimating” together with the SP value obtained by the method.
both the Solubility Parameters and
Molecular Volumes of Liquids,
POLYMER ENGINEERING AND SCIENCE,
FEBRUARY, 1974, vol. 14, Issue 2, p. 147-154 ", and these can be used in the present invention.

  Examples of the adherend include a polyester resin, a polycarbonate resin, a polyamide resin, and a mixture of two or more thereof. Examples of the form of the adherend include a plate shape, a sheet shape, a film, and a fiber (including a nonwoven fabric).

  Examples of the method of applying the hot melt adhesive of the present invention include, but are not limited to, methods such as spiral coating, bead coating, roll coating, and slot coating. Moreover, the melting temperature when applied is usually 100 to 200 ° C., the melt viscosity is usually 1 to 500 Pa · s, and preferably 2 to 100 Pa · s from the viewpoint of coating properties.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”.

[Polyolefin (A)]
Production Example 1
Polyolefin (A0-1) having a structural unit of 98 mol% propylene and 2 mol% ethylene in a reaction vessel [trade name “Sun Allomer PZA20A”, manufactured by Sun Allomer Co., Ltd., Mn 100,000, molecules per 1,000 carbons The number of double bonds in the terminal and / or molecular chain is 0, and so on. 100 parts were charged in a nitrogen atmosphere, heated and melted with a mantle heater while nitrogen was passed through the gas phase portion, and subjected to heat degradation at 360 ° C. for 70 minutes while stirring to obtain polyolefin (A-1). . In (A-1), the number of double bonds in molecular ends and / or molecular chains per 1,000 carbon atoms was 7.2, and Mn was 3,000.

Production Examples 2-6
Except having performed thermal degradation according to Table 1 in the manufacture example 1, it carried out similarly to the manufacture example 1 and obtained polyolefin (A-2)-(A-6). The results are shown in Table 1.

[Production of copolymer]
Production Example 7
A reaction vessel was charged with 100 parts of (A-1), 24 parts of maleic anhydride (B-1), 18.5 parts of 1-decene (C-1) and 100 parts of xylene. The mixture was heated to 130 ° C. and dissolved uniformly. A solution prepared by dissolving 0.5 part of dicumyl peroxide [trade name “Park Mill D”, manufactured by NOF Corporation] (D-1) in 10 parts of xylene was added dropwise over 10 minutes, and then refluxed with xylene. Stirring was continued for 3 hours. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain a copolymer (X-1). (X-1) had an acid value of 95 and Mn of 5,000.

Production Examples 8 to 27, Comparative Production Examples 1 to 8
In Production Example 7, in accordance with Tables 2 and 3, except that each used raw material was used, the same procedure as in Production Example 7 was carried out, and copolymers (X-2) to (X-21), (RX-1) to (RX-1) to ( RX-8) was obtained. The results are shown in Tables 2 and 3.

[Hot melt adhesive]
Example 1
80 parts of the obtained copolymer (X-1) and tackifying resin [partially hydrogenated petroleum resin [C9 fraction copolymer main component, “Arcon M-115”, manufactured by Arakawa Chemical Co., Ltd.] The same shall apply hereinafter.) (E-1) 20 parts are blended, the temperature of the heating medium of the jacket is set to 160 ° C., the diameter D is 1 inch, and the screw shaft length L is 10 inches (L / D ratio = 10). A hot-melt adhesive (H-1) containing (X-1) is obtained by melt-kneading using a heat-melting kneader ["KRC S1", manufactured by Kurimoto Tekko Co., Ltd.] capable of continuous mixing. Obtained. About the obtained hot-melt-adhesive (H-1), fluidity | liquidity and T-type peeling adhesive strength were evaluated with the following test method. The results are shown in Table 4.

Examples 2-22, Comparative Examples 1-8
In Example 1, it carried out similarly to Example 1 except having used each use raw material according to Table 4, 5, hot melt adhesive (H-2)-(H-22), (RH-1)-( RH-8) was obtained. About each obtained hot-melt-adhesive, it carried out similarly to Example 1, and evaluated fluidity | liquidity and T-type peeling adhesive strength. The results are shown in Tables 4 and 5.

(1) Fluidity test (evaluation of coatability)
A test piece was prepared by cutting the hot melt adhesive into a length of 10 mm, a width of 10 mm, and a thickness of 5 mm using an ultrasonic cutter. A double-sided tape was attached to a polypropylene plate having an inclination angle of 45 °, and was allowed to stand for 5 minutes in an atmosphere at a temperature of 120 ° C., and the distance that the test piece flowed from the initial position was measured (unit: mm).

(2) T-type peel adhesion strength (adhesion evaluation)
A hot melt adhesive was applied to one side of a polypropylene nonwoven fabric (hereinafter abbreviated as PPNW) having a length of 150 mm, a width of 25 mm, and a thickness of 0.5 mm (adhesive temperature of 150 ° C., coating amount of 0.04 g / m ^2). And a polyethylene terephthalate film (hereinafter abbreviated as PET) was stacked and bonded at 120 ° C. under a load of 500 g / m ² . Then, after standing at 25 ° C. for 24 hours, the peel strength was measured at a tensile rate of 300 mm / min using an autograph in accordance with JIS K6854-3, and the maximum peel strength was determined as a T-type peel bond. Strength was used (unit: g / 25 mm).

  From the results of Tables 4 and 5, the hot melt adhesive (H) of the present invention has excellent coatability compared to the comparative one, and is a highly polar adherend with a polyolefin resin molded article or the like. It turns out that it has the outstanding adhesiveness with respect to it.

  Since the hot melt adhesive of the present invention is excellent in coating properties and adhesion between a polyolefin resin molded article and the like and an adherend having a high polarity, a wide range of adherends (for example, various plastic molded articles, rubber, paper) , Cloth, metal, wood, glass, mortar concrete), which is very useful.

Claims (9)

  A hot melt adhesive comprising a copolymer (X) having a polyolefin (A) and an unsaturated (poly) carboxylic acid (anhydride) (B) as a structural unit and an acid value of 50 to 250 mgKOH / g ( H).   The adhesive according to claim 1, wherein (B) is an unsaturated dicarboxylic acid (anhydride).   Furthermore, the adhesive agent of Claim 1 or 2 which adds an aliphatic unsaturated hydrocarbon (C) to the structural unit of copolymer (X).   The adhesive according to any one of claims 1 to 3, wherein (X) is a graft copolymer in which (A) is a trunk and (B) or a (co) polymer of (B) and (C) is a branch. .   The adhesive according to any one of claims 1 to 4, wherein (A) has 0.1 to 20 double bonds per 1,000 carbon atoms.   The adhesive according to any one of claims 1 to 5, wherein (A) is a thermal degradation product of a polyolefin (A0) having a number average molecular weight of 30,000 to 400,000.   The weight ratio of (A) and (B) is 30 / 70-92 / 8, The adhesive agent in any one of Claims 1-6.   Content based on the total weight of (A), (B) and (C) is (A) 20-85%, (B) 8-45%, (C) 5-65%. The adhesive in any one of 3-7.   The adhesive according to any one of claims 1 to 8, further comprising a tackifying resin (E).