JP2016011413A - Modifier for polyolefin resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modifier for a polyolefin resin that imparts excellent wettability to water to a polyolefin resin base material without impairing mechanical strength.SOLUTION: The modifier for a polyolefin resin comprises: a modified polyolefin having at least one kind of functional group selected from the group consisting of an acid anhydride group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, an amino group and a thiol group; and a sulfonic acid (salt)-modified polyolefin produced from the modified polyolefin and a sulfonic acid (salt) group-containing compound having a reactive functional group. A polyolefin resin composition comprises the modifier and a polyolefin resin. A molded article is produced by molding the composition.

Description

  The present invention relates to a modifier for polyolefin resins. More specifically, the present invention relates to a polyolefin resin modifier containing a sulfonic acid (salt) -modified polyolefin.

Polyolefin resins are excellent in moldability, rigidity, heat resistance, chemical resistance, electrical insulation, and the like, and are inexpensive, so they are widely used as films, fibers, and other shaped articles of various shapes. On the other hand, a polyolefin resin is a so-called nonpolar and extremely inert polymer substance having no polar group in the molecule. In addition, since it has high crystallinity and extremely low solubility in solvents, there are problems such as adhesion and paintability, and poor wettability with water and water repellent, so that water-based paint cannot be applied. It was.
Conventionally, as a method for improving wettability, a surface of a thermoplastic resin base material, for example, a polyolefin resin molded product, is subjected to corona treatment or plasma treatment (for example, see Patent Document 1), and a surfactant is added to the polyolefin resin composition. A method of adding and making this into a molded product (for example, see Patent Document 2) is known.

JP 2000-319426 A JP 2004-169014 A

However, the method of subjecting the surface of the molded product to corona treatment or plasma treatment has a problem that wettability decreases with the passage of time after treatment. In addition, in the method of adding a surfactant to a polyolefin resin composition and making this into a molded product, the mechanical strength inherent to the original molded product of the polyolefin resin substrate can be obtained by adding an amount sufficient to exert a modification effect. (Tensile elastic modulus, impact resistance, etc .; the same shall apply hereinafter) is impaired, and the surfactant bleeds out of the molded product, and there is a problem that wettability decreases with the passage of time. .
An object of the present invention is to provide a polyolefin resin modifier that imparts excellent wettability to water to a polyolefin resin substrate without impairing mechanical strength.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention relates to a modified polyolefin (A) having at least one functional group selected from the group consisting of acid anhydride groups, epoxy groups, isocyanate groups, carboxyl groups, hydroxyl groups, amino groups, and thiol groups, and (A ) And a sulfonic acid (salt) group-containing compound (B) having a functional group reactive with the polyolefin resin modifier (K) comprising the sulfonic acid (salt) modified polyolefin (X); A polyolefin resin composition comprising (K) and a polyolefin resin (D); a molded article formed by molding the composition.
In the present invention, sulfonic acid (salt) means sulfonic acid and / or sulfonate.

The polyolefin resin modifier (K) of the present invention has the following effects.
(1) It is excellent in the modification property which gives wettability (polarity) to water and its sustainability to polyolefin resin without impairing mechanical strength.
(2) The molded article of the polyolefin resin composition containing the modifier is excellent in water wettability and mechanical strength.

[Modified polyolefin (A)]
The modified polyolefin (A) in the present invention is a polyolefin having at least one functional group selected from the group consisting of an acid anhydride group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, an amino group, and a thiol group. The polyolefin (a0) is modified to have the functional group.

  The polyolefin (a0) includes one or more (co) polymers of olefins, and a copolymer of one or more olefins and one or more other monomers. 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 styrene and vinyl acetate.

  Specific examples of (a0) 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 from the viewpoint of moldability of polyolefin resin composition and heat resistance of molded product) To preferably 30/70 to 99/1, more preferably 50/50 to 95/5); propylene unit-containing (ethylene unit-free) (co) polymers such as polypropylene, propylene and C4-30 unsaturated Copolymer with monomer (same as above) (weight ratio is the same as above); ethylene / propylene copolymer (weight ratio is the moldability of polyolefin resin composition and heat resistance of molded product) From the point, preferably 0.5 / 99.5 to 30/70, more preferably 2 / 98-20 / 80); it contains C4 and higher olefins (co) polymers, such as polybutene. Among these, polyethylene, polypropylene, ethylene / propylene copolymer, propylene / C4-30 unsaturated monomer copolymer, and more preferably from the viewpoint of compatibility with the polyolefin resin (D) described later. An ethylene / propylene copolymer and a propylene / C4-30 unsaturated monomer copolymer.

  Weight average molecular weight of the polyolefin (a0) [hereinafter abbreviated as Mw. The measurement is based on a gel permeation chromatography (GPC) method measured under the conditions described later. ] Is preferably 1,000 to 500,000, more preferably 2,000 to 450,000, and particularly preferably 4,000 to 400,000 from the viewpoint of the modification properties of the polyolefin resin modifier (K) described later. From the same viewpoint, the number average molecular weight (hereinafter abbreviated as Mn, measured by the GPC method as in Mw) is preferably 500 to 250,000, more preferably 1,000 to 225,000. Preferably it is 2,000-200,000.

The measurement conditions for GPC in the present invention are as follows.
<GPC measurement conditions>
[1] Apparatus: Waters 150-CV [manufactured by Waters Co., Ltd.]
[2] Column: PLgel 10. MIXED-B
[Made by Polymer Laboratories, Inc.]
[3] Eluent: o-dichlorobenzene [4] Reference material: polystyrene [5] Injection conditions: sample concentration 3 mg / ml, column temperature 135 ° C.

The polyolefin (a0) preferably has a double bond in the molecular end and / or in the molecular chain from the viewpoint of ease of modification with the functional group described below. The number of double bonds in the molecular ends and / or molecular chains per 1,000 carbons of (a0) [the number of double bonds per 1,000 carbons. In the following, it is preferably 0.01 to 40, more preferably 0.02 to 35, and particularly preferably 0 from the viewpoint of ease of modification of (a0) and productivity of the modifier (K). 0.03 to 30.
Here, the number of double bonds can be determined from the spectrum of (a0) ¹ H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peak in the spectrum is assigned, and the number of double bonds of (a0) and the value of (a0) are calculated from the integral value derived from the double bond at 4.5 to 6 ppm of (a0) and the integral value derived from (a0). Is calculated, and the number of double bonds in the molecular end and / or molecular chain per 1,000 carbon atoms of (a0) is calculated. The number of double bonds in the examples described later followed this method.

  The polyolefin (a0) is produced by a polymerization method (for example, those described in JP-A-59-206409 and JP-A-55-13502) and a degradation method [thermal, chemical and mechanical reduction. Among these methods, the thermal degradation method (hereinafter sometimes referred to as the thermal degradation method) includes, for example, JP-B 43-9368, JP-B 44-29742, and JP-B 6-70094. Those described in the publication].

  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, the high molecular weight obtained by the polymerization method (Mw 100,000 to 600,000)
Include methods of thermally, chemically or mechanically degrading the polyolefins.

  Among the degradation methods, in the thermal degradation method, the polyolefin is aerated with nitrogen and (1) in the absence of an organic peroxide (for example, dicumyl peroxide, the same shall apply hereinafter), usually at 300 to 450 ° C. A method of thermally degrading continuously or discontinuously for 0.5 to 10 hours, and (2) continuously or discontinuously at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide. Includes a method for heat degradation. Among these, the method (1) is preferable from the viewpoint that a compound having a larger number of double bonds in the molecular terminal and / or molecular chain can be easily obtained and the modification of (a0) is easy.

  Of these production methods of (a0), those having a larger number of double bonds in the molecular end and / or molecular chain are easily obtained, and from the viewpoint of easy modification of (a0) in the subsequent step, it is preferable to reduce the production method. A synthesis method, more preferably a thermal degradation method, is preferred.

  The modified polyolefin (A) has, for example, at least one functional group selected from the group consisting of the polyolefin (a0) and an acid anhydride group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, an amino group, and a thiol group. The polymerizable unsaturated monomer (c) can be produced by reacting in the presence or absence of the radical initiator (s).

The polymerizable unsaturated monomer (c) includes the following (c1) to (c6).
Examples of the polymerizable unsaturated monomer (c1) having an acid anhydride group include unsaturated poly (n = 2 to 3, preferably 2) carboxylic acid anhydrides having one polymerizable unsaturated group.
The (c1) includes C4-30, such as aliphatic (C4-24, such as maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, and aconitic anhydride), and fat And cyclic ones (C8-24, such as cyclohexene dicarboxylic acid anhydride, cycloheptene dicarboxylic acid anhydride). Among these (c1), from the viewpoint of the modification properties of the polyolefin resin modifier (K) described later, an aliphatic unsaturated dicarboxylic acid anhydride is preferable, and maleic anhydride is more preferable.

  As the polymerizable unsaturated monomer (c2) having an epoxy group, C6-100, for example, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, poly (glycidyl ether) mono (meta) ) Acrylates. The poly (glycidyl ether) in the mono (meth) acrylate of the poly (glycidyl ether) is an alkyl glycidyl ether, alkenyl glycidyl ether or aromatic ring-containing glycidyl ether having a C1-12 alkyl group, alkenyl group or aromatic ring. Examples include polymers obtained by ring-opening polymerization of each glycidyl group. Examples of the alkyl glycidyl ether include ethyl glycidyl ether, n-propyl glycidyl ether, n- and i-butyl glycidyl ether, n-hexyl glycidyl ether, and 2-ethylhexyl glycidyl ether; Ether, propenyl glycidyl ether and the like; Examples of the aromatic ring-containing glycidyl ether include phenyl glycidyl ether and the like. The number of glycidyl ether units of the poly (glycidyl ether) is preferably 2 to 20, more preferably 2 to 10 from the viewpoint of the modifying properties of the modifier (K), and the poly (glycidyl ether) mono (meta) ) The molecular weight of the acrylate is preferably 202 to Mw 2,000, more preferably 202 to Mw 1,000 from the same viewpoint. Of these (c2), glycidyl (meth) acrylate is preferred from the viewpoint of the modification properties of (K).

  Examples of the polymerizable unsaturated monomer (c3) having an isocyanate group include C3-10, such as 2-isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylmethylbenzyl isocyanate and vinyl isocyanate. Of these (c3), 2-isocyanate ethyl (meth) acrylate and vinyl isocyanate are preferred from the viewpoint of the modifying properties of the modifier (K), and 2-isocyanate ethyl (meth) acrylate is more preferred. .

  As the polymerizable unsaturated monomer (c4) having a carboxyl group, C3-20 unsaturated carboxylic acid [(meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, etc.] And unsaturated carboxylic acid ester [monoalkyl maleate (C1-3) ester, monoalkyl fumarate (C1-3) ester, monoalkyl itaconic acid (C1-3) ester, monoalkyl citraconic acid (C1-3) Ester, etc.]. Of these (c4), (meth) acrylic acid, maleic acid and itaconic acid are preferred from the viewpoint of the modifying properties of the modifier (K), and (meth) acrylic acid is more preferred.

  Examples of the polymerizable unsaturated monomer (c5) having a hydroxyl group include the following (c51) to (c56).

(C51) Hydroxyl group-containing (meth) acrylate (c51) (c511) (meth) acrylate represented by the following general formula (1), (c512) polyhydric alcohol having 3 to 8 hydroxyl groups described later (Meth) acrylate is mentioned.

^{_{CH 2 = CR 1 -C (=}} O) O- (A-O) m H (1)

In the general formula (1), R ¹ represents H or a methyl group, A represents a C2-4 alkylene group, and m represents a number of 1 to 20 (preferably 1 to 10, more preferably 1). ]

  (C511) includes hydroxyalkyl (C2-4) (meth) acrylate [2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA), 2-hydroxypropyl (meth) Acrylate, 3-hydroxypropyl (meth) acrylate, etc.], and hydroxyalkoxy (C2-4) alkyl (meth) acrylate [2-hydroxyethoxyethyl (meth) acrylate, etc.];

(C512) (Meth) acrylates of polyhydric alcohols having 3 to 8 hydroxyl groups Examples of polyhydric alcohols include C3-12 alkane polyols, intramolecular or intermolecular dehydrates, and sugars [for example, glycerin, trimethylol. Propane, pentaerythritol, sorbitol (hereinafter abbreviated as GR, TMP, PE, SO), sorbitan, diGR, sucrose, methylglucoside], and (meth) acrylates thereof include GR mono- and di- (meta ) Acrylate, TMP mono- and di- (meth) acrylate, sucrose (meth) acrylate, etc .;

(C52) C2-12 alkenol vinyl alcohol (formed by hydrolysis of vinyl acetate units), and C3-12 alkenol [(meth) allyl alcohol, (iso) propenyl alcohol, crotyl alcohol, 1-butene -3-ol, 1-buten-4-ol, 1-octenol, 1-undecenol, 1-dodecenol and the like];
(C53) C4-12 alkenediol, 2-butene-1,4-diol and the like;

(C54) a hydroxyl group-containing alkenyl ether having an alkenyl group of C3-12, such as a hydroxyalkyl (C1-6) alkenyl ether [for example, 2-hydroxyethylpropenyl ether, and the alkenyl of the polyhydric alcohol described in (c512) above (C3 -12) ether [TMP mono- and di- (meth) allyl ether, sucrose (meth) allyl ether, etc.]];
(C55) a hydroxyl group-containing aromatic monomer o-, m-, p-hydroxystyrene and the like;
(C56) At least one of the hydroxyl groups of the (poly) oxyalkylene ethers (c51) to (c55) in the above (c51) to (c55) is substituted with —O (A—O) _m —A—OH. Monomer [where A and m are the same as those in the general formula (1)].

  Of (c5), from the viewpoint of the modifying properties of the modifier (K), (c51), (c52), (c54), (c55) and (c56) are preferred, and (c511) is more preferred. Particularly preferred are HEA and HEMA, and most preferred is HEMA.

  Examples of the polymerizable unsaturated monomer (c6) having an amino group include those of C3 to C20, such as primary amino group-containing vinyl monomers [alkenyl (C3-6) amine [(meth) allylamine, crotylamine etc.] and aminoalkyl ( C2-6) (meth) acrylate [aminoethyl (meth) acrylate etc.] etc.]; secondary amino group-containing vinyl monomer [alkyl (C1-6) aminoalkyl (C2-6) (meth) acrylate [t-butylamino] Ethyl methacrylate, methylaminoethyl (meth) acrylate and the like], 2- and 4-diphenylamine (meth) acrylamide, C6-12 dialkenylamine [di (meth) allylamine and the like] and the like. Of these (c6), aminoethyl (meth) acrylate is preferred from the viewpoint of the modifying properties of the modifier (K).

  Examples of the polymerizable unsaturated monomer (c7) having a thiol group include C4-10, such as vinyl-2-ethylmercaptoethyl ether and 2-mercaptoethyl (meth) acrylate.

  The polymerizable unsaturated monomer (c) may be used alone or in combination of two or more. Of these (c), preferred from the viewpoint of the modifying properties of the modifier (K) are (c1), (c2), (c5), (c6) and (c7), and more preferably Aliphatic unsaturated dicarboxylic acid anhydride, glycidyl (meth) acrylate, allyl glycidyl ether, HEA, HEMA, aminoethyl (meth) acrylate and 2-mercaptoethyl (meth) acrylate, particularly preferred are maleic anhydride, glycidyl (meta) ) Acrylate, HEMA and aminoethyl (meth) acrylate.

  The weight ratio [(a0) / (c)] of (a0) and (c) in the production of the polyolefin (A) is the compatibility with the polyolefin resin (D) described later and the modification of the modifier (K). From the viewpoint of characteristics, it is preferably 30/70 to 99/1, more preferably 50/50 to 97/3, and particularly preferably 70/30 to 95/5.

Specific methods for producing the modified polyolefin (A) obtained by modifying with the polymerizable unsaturated monomer (c) include the following methods [1] and [2].
[1] Heat-melting polyolefin (a0) and polymerizable unsaturated monomer (c), or a suitable organic solvent [C2-18, such as hydrocarbons (for example, hexane, heptane, octane, decane, dodecane, benzene, toluene and xylene) ), Halogenated hydrocarbons (eg di-, tri- and tetrachloroethane and dichlorobutane), ketones (eg acetone, methyl ethyl ketone, diethyl ketone and di-t-butyl ketone) and ethers (eg ethyl-n-propyl ether, di- i-propyl ether, di-n-butyl ether, di-t-butyl ether and dioxane). same as below. The radical initiator (s) [or (s) is dissolved in a suitable organic solvent (same as above). same as below. ] A chain transfer agent (t) and a polymerization inhibitor (u) described later are added and heated and stirred (melting method, suspension method and solution method);
[2] A method in which (a0), (c) and, if necessary, (s), (t), (u) are melt-mixed in advance and melt-kneaded using an extruder, a Banbury mixer or a kneader (melt-kneading method) .
Among these, the method [1] is preferable from the viewpoint of the reactivity between (a0) and (c), and the melting method and the solution method are more preferable.

  The reaction temperature in the melting method may be a temperature at which (a0) melts, and is preferably 120 to 260 ° C. from the viewpoint of the reactivity between (a0) and (c) and the thermal stability of (A). Preferably it is 130-240 degreeC.

  Examples of the radical initiator (s) in the present invention include azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.) and 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, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, di-t-butylperoxyhexahydroterephthalate, diallyl peroxydicarbonate, t -Butyl peroxyallyl carbonate and the like]]. Among these, from the viewpoint of the reactivity between (a0) and (c), a peroxide is preferable, a monofunctional peroxide is more preferable, and di-t-butyl peroxide and lauroyl peroxide are particularly preferable. And dicumyl peroxide.

  The amount of the radical initiator (s) used is preferably 0.001 to 20 based on the weight of the polymerizable unsaturated monomer (c) and from the viewpoint of reactivity between (a0) and (c) and suppression of side reactions. %, More preferably 0.01 to 10%, particularly preferably 0.1 to 5%.

  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, 1-octanethiol); aldehydes (C2-18, such as n- and sec-butyraldehyde, 1-pentylaldehyde); phenols (C6-36, such as phenol, o-, m- and p-cresol) ); Amines (C3-24, such as diethyl methylamine, triethylamine, diphenylamine); disulfides (C2-24, such as diethyl disulfide, di-1-propyl disulfide). The amount of (t) used is usually 40% or less based on the weight of the polymerizable unsaturated monomer (c), the reactivity between (a0) and (c) and the compatibility between (a0) and (t). From the viewpoint, it is preferably 0.05 to 20%.

  Examples of the polymerization inhibitor (u) include inorganic compounds [eg, oxygen, sulfur and metal salts (such as ferric chloride)] and organic compounds [catechol (C6-36, eg, 2-methyl-2-propylcatechol), quinone (C6-24, such as p-benzoquinone and duroquinone), hydrazine (C2-36, such as 1,1-diphenyl-2-picrylhydrazine), ferrazine (C5-36, such as 1,3,5-triphenyl ferrazine) ), Nitro compounds (C3-24, such as nitrobenzene) and stable radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6-tetramethyl-1- Piperidinyloxy (TEMPO) and 1,3,5-triphenylferdazyl] and the like. The amount of (u) used is usually 5% or less based on the weight of the polymerizable unsaturated monomer (c), and is preferably from the viewpoint of the stability of (a0) and (c) and the productivity of (A). 01 to 0.5%.

  The modified polyolefin (A) can be produced by reacting the polyolefin (a0) and the polymerizable unsaturated monomer (c) in the presence or absence of the radical initiator (s) as described above. Further, an acid-modified product (a01) obtained by reacting a polyolefin (a0) with an unsaturated polycarboxylic acid and / or an acid anhydride (f) thereof in the same manner as in the reaction of (a0) and (c), An active hydrogen atom-containing compound (g) having at least two functional groups selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, and a reaction equivalent ratio of (g) and (a01) [(g ) / (A01)] can also be produced by reacting so as to exceed 1.

  Among the unsaturated polycarboxylic acid anhydrides in (f), the unsaturated polycarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cyclohexenedicarboxylic acid anhydride, and aconitic acid anhydride are exemplified. Can be mentioned. (F) may be used alone or in combination of two or more. Of these (f), an anhydride of an unsaturated dicarboxylic acid is preferred, and maleic anhydride is more preferred from the viewpoint of the modifying properties of the modifier (K) and the reactivity with (a0).

  The weight ratio [(a0) / (f)] between (a0) and (f) when modifying (a0) with (f) is compatible with the polyolefin resin (D) and the modification of the modifier (K). From the viewpoint of quality characteristics, it is preferably 80/20 to 99/1, more preferably 83/17 to 98/2, and particularly preferably 85/15 to 95/3. The unreacted (f) in the acid-modified product (a01) is preferably 10% by weight or less, more preferably 1% by weight or less, particularly preferably 0.1% by weight from the viewpoint of the mechanical strength of the molded product described later. It is as follows.

  (A0) and (f) can be reacted in the presence or absence of the radical initiator (s), but from the viewpoint of the reactivity between (a0) and (f) (s ) In the presence of. Examples of (s) include those described above, and preferable ones among them are also the same.

  The amount of (s) used is preferably 0.001%, more preferably 0.01%, particularly preferably 0, based on the weight of (f), from the viewpoint of the reactivity of (a0) and (f). .1%, and the upper limit is preferably 100%, more preferably 50%, particularly preferably 30% from the viewpoint of side reaction suppression.

Specific methods for producing the acid-modified product (a01) include the following methods [1] and [2].
[1] (a0) and (f) are heated and melted, or suspended or dissolved in a suitable organic solvent (the same as above), and if necessary, the above (s), (t), (u) And heating and stirring (melting method, suspension method and solution method);
[2] A method (melt kneading method) in which (a0), (f) and, if necessary, (s), (t), (u) are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like. included.
Among these, the method [1] is preferable from the viewpoint of the reactivity between (a0) and (f), and the melting method and the solution method are more preferable.

  The reaction temperature in the melting method may be a temperature at which (a0) melts, and is preferably 120 to 260 from the viewpoint of the reactivity between (a0) and (f) and the thermal stability of the acid-modified product (a01). ° C, more preferably 130-240 ° C.

  The reaction temperature in the solution method may be any temperature at which (a0) is dissolved in a solvent, and is preferably from the viewpoint of the reactivity between (a0) and (f) and the thermal stability of the acid-modified product (a01). 50-220 degreeC, More preferably, it is 110-210 degreeC, Most preferably, it is 120-180 degreeC.

  The active hydrogen atom-containing compound (g) includes at least one compound selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, and a compound having two or more functional groups having reactivity with the acid-modified product (a01). included. Specific examples of the compound (g) include the following, and one or a mixture of two or more thereof can be used.

  Examples of the active hydrogen atom-containing compound (g1) having two or more hydroxyl groups include polyhydric alcohols such as dihydric alcohols [(poly) ethylene glycol [ethylene glycol, polyoxyethylene glycol (degree of polymerization: 2 to 200)], (Poly) propylene glycol [propylene glycol, polyoxypropylene glycol (polymerization degree 2 to 180)], (poly) tetramethylene glycol [1,4-butanediol, polyoxytetramethylene glycol (polymerization degree 2 to 150) And 1,4-bis (hydroxymethyl) cyclohexane etc.]; trihydric alcohol [GR and TMP etc.], tetrahydric alcohol [PE and sorbitan etc.], pentahydric alcohol (eg glucose and fructose etc.), hexavalent alcohol [ SO, xylitol, mannitol, di-PE And tetra-GR, etc.], 7-valent alcohol (such as penta-GR), 8-valent alcohol (such as sucrose, hexa-GR and tri-PE), 9-valent alcohol (such as hepta GR), 10-valent alcohol (such as octa-GR); polymerization Oligomers of 2 to 10 or more degrees (polyvinyl alcohol, poly (meth) allyl alcohol, polyhydroxyethyl (meth) acrylate and polyhydroxypropyl (meth) acrylate etc.), 6 to 10 or more urethanized polyols and Polyester polyol (for example, a reaction product of the above polyhydric alcohol with a polyisocyanate or polycarboxylic acid compound), a reaction product of a polyol having 2 to 8 or more hydroxyl groups per molecule and a diepoxy compound [for example, JP-B-46 Described in Japanese Patent No. 24255, Examples of the diepoxy compound include bisphenol A type epoxy resin, cycloaliphatic diepoxide (1-epoxyethyl-3,4-epoxycyclohexane, etc.), polyoxyalkylene (alkylene group is C2-4, polymerization degree 2-100) type epoxy. Resin, tertiary amino group-containing polyol (AO adducts such as triisopropanolamine, triethanolamine, morpholine, etc.)] and the like.

  Examples of the active hydrogen atom-containing compound (g2) having two or more amino groups (primary or secondary, the same shall apply hereinafter) include diamines (ethylenediamine and the like), polyalkylene (C2-6) polyamines having 3 to 8 amino groups ( Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.), branched polyethyleneimine, polyamide polyamine (for example, a condensate of dimer acid and the above polyalkylene polyamine described in JP-B-51-44275) Is mentioned.

  Examples of the active hydrogen atom-containing compound (g3) having at least one amino group and hydroxyl group include hydroxylamine, hydroxyalkylated (C2-4) of primary monoamine, and primary monoamine and alkylated thereof (C1 to C1). 4) Alkylene oxide (hereinafter abbreviated as AO) adducts [mono- and dihydroxyalkylamines (mono- and diethanolamine, mono- and diisopropanolamine), ethylamine AO adducts, etc.].

  As the active hydrogen atom-containing compound (g4) having two or more thiol groups, a 2 to 10 functional or higher thiol obtained by the reaction of the polyhydric alcohol and thiourea, a 1 to 10 mer of epichlorohydrin, or 2-10 functional or more thiol etc. which are obtained by reaction with more and sodium hydrosulfide are mentioned.

  Of these, dihydric alcohol, hydroxylamine, and diamine are preferable from the viewpoint of the modifying properties of the modifier (K), and ethylene glycol, mono- and diethanolamine, and ethylenediamine are more preferable.

  In the above production method of (A), the reaction equivalent ratio [(g) / (a01)] of the active hydrogen atom-containing compound (g) and the acid-modified product (a01) is the reforming property of the modifier (K). From the viewpoint of compatibility with the polyolefin resin (D), the ratio is preferably 1.1 / 1 to 5/1, more preferably 1.5 / 1 to 3/1.

Examples of the method for producing the modified polyolefin (A) by reacting the acid-modified product (a01) with the active hydrogen atom-containing compound (g) include the following methods [1] and [2].
[1] A method in which (a01) and (g) are heated and melted, or suspended or dissolved in an appropriate organic solvent (the same as above), and heated and stirred (melting method, suspension method and solution method);
[2] A method in which (a01) and (g) are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like (melt-kneading method).
Among these, the method [1] is preferable from the viewpoint of the reactivity between (a01) and (g), and the melting method and the solution method are more preferable.

  The reaction temperature in the melting method may be a temperature at which (a01) melts, and is preferably 120 to 260 ° C, more preferably 130 to 240 ° C from the viewpoint of the reactivity between (a01) and (g). .

  The reaction temperature in the solution method may be a temperature at which (a01) is dissolved in a solvent, and is preferably 50 to 220 ° C. from the viewpoint of the reactivity between (a01) and (g) and the thermal stability of (A). More preferably, it is 110-210 degreeC, Most preferably, it is 120-180 degreeC.

  The Mw of the modified polyolefin (A) is preferably 1,000 to 500,000, more preferably 2,000 to 450, from the viewpoint of the mechanical strength of the molded product described later and the moldability of the polyolefin resin composition described later. 000.

  As described above, the modified polyolefin (A) has at least one functional group selected from the group consisting of an acid anhydride group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, an amino group, and a thiol group. ) The number of functional groups per molecule is preferably 1 to 50, more preferably 2 to 30 from the viewpoint of the modifying properties of the modifier (K) and compatibility with the polyolefin resin (D) described later. It is a piece.

[Sulfonic acid (salt) group-containing compound (B)]
The sulfonic acid (salt) group-containing compound (B) in the present invention is a sulfonic acid (salt) group-containing compound having a functional group reactive with the (A). Examples of (B) include the following (B1) to (B4).

Sulfonic acid (salt) group-containing compound (B1) having a hydroxyl group:
(B1) includes those having 1 to 2 hydroxyl groups in the molecule, for example, 3-hydroxypropanesulfonic acid alkylene oxide adduct, 3-hydroxypropanesulfonic acid sodium salt alkylene oxide adduct, 3-hydroxypropanesulfonic acid Potassium salt alkylene oxide adduct, 3-hydroxypropanesulfonic acid ammonium salt alkylene oxide adduct, 2-hydroxyethanesulfonic acid, 2-hydroxyethanesulfonic acid lithium salt, 2-hydroxyethanesulfonic acid sodium salt, 2-hydroxyethanesulfone Acid potassium acid, 2-hydroxyethanesulfonic acid ammonium salt, 3-hydroxypropanesulfonic acid, 3-hydroxypropanesulfonic acid lithium salt, 3-hydroxypropanesulfonic acid sodium salt, -Potassium hydroxypropanesulfonic acid, ammonium salt of 3-hydroxypropanesulfonic acid, isethionic acid, lithium isethionic acid, sodium isethionic acid, potassium isethionic acid, ammonium isethionic acid, 2- [4- (2-hydroxyethyl) ) -1-piperazinyl] ethanesulfonic acid, 2- [4- (2-hydroxyethyl) -1-piperazinyl] ethanesulfonic acid lithium salt, 2- [4- (2-hydroxyethyl) -1-piperazinyl] ethanesulfone Acid sodium salt, 2- [4- (2-hydroxyethyl) -1-piperazinyl] ethanesulfonic acid potassium salt, 2- [4- (2-hydroxyethyl) -1-piperazinyl] propanesulfonic acid, N- (Tris Hydroxymethyl) methyl-2-aminoethanesulfonic acid 2-hydroxy-3-morpholinopropanesulfonic acid, p-phenolsulfonic acid, N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid sodium salt, 1-amino-8-naphthol-4-sulfonic acid, 6- Examples include amino-1-naphthol-3-sulfonic acid and 3-amino-4-hydroxybenzenesulfonic acid.
In the above (B1), the alkylene oxide adduct is a product obtained by reacting a hydroxyl group with an alkylene oxide (having 2 to 4 carbon atoms, for example, ethylene oxide or 1,2-propylene oxide) (addition number is 1 to 20). It is.

Amino group-containing sulfonic acid (salt) group-containing compound (B2):
(B2) includes those having 1 to 2 amino groups in the molecule, such as aminomethanesulfonic acid, 2-aminoethylsulfonic acid, 3-aminopropylsulfonic acid, N-methyltaurine sodium salt, N- (2 -Acetamido) 2-aminoethanesulfonic acid, N-cyclohexylaminoethanesulfonic acid, cysteic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, sulfanilic acid, m-toluidine-4-sulfonic acid, p-toluidine 2-sulfonic acid, o-anisidine-5-sulfonic acid, m-anisidine-2-sulfonic acid, p-anisidine-2-sulfonic acid, 4-amino-1-naphthalenesulfonic acid, 5-amino-1-naphthalene Sulfonic acid, 5-amino-2-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfone 6-amino-2-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 1,3-phenylenediamine-4-sulfonic acid, 7-amino-1,3-naphthalenedisulfonic acid monopotassium salt, 3- Amino-2,7-naphthalenedisulfonic acid monopotassium salt, 2,2′-benzidine disulfonic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, 3,5-diamino-2,4,6- Examples include trimethylbenzenesulfonic acid.

Carboxylic acid (salt) group-containing compound (B3) having a carboxyl group:
(B3) includes those having 1 to 2 carboxyl groups in the molecule, such as 2-sulfobenzoic acid, 3-sulfobenzoic acid, 4-sulfobenzoic acid, 2-sulfobenzoic acid monolithium salt, 2-sulfo Benzoic acid monosodium salt, 2-sulfobenzoic acid monopotassium salt, 2-sulfobenzoic acid monoammonium salt, 3-sulfobenzoic acid monolithium salt, 3-sulfobenzoic acid monosodium salt, 3-sulfobenzoic acid monopotassium salt 3-sulfobenzoic acid monoammonium salt, 4-sulfobenzoic acid monosodium salt, 4-sulfobenzoic acid monopotassium salt, 4-sulfobenzoic acid monoammonium salt, 2-sulfoterephthalic acid, 2-sulfoterephthalic acid lithium salt 2-sulfoterephthalic acid sodium salt, 2-sulfoterephthalic acid potassium salt, 2-sulfoterephthalic acid Ammonium salt, 3-sulfoisophthalic acid, 3-sulfoisophthalic acid lithium salt, 3- sulfoisophthalic acid sodium salt, 3-sulfoisophthalic acid potassium salt, 3-sulfoisophthalic acid ammonium salts.

Sulfonic acid (salt) group-containing compound (B4):
(B4) is a compound having at least two structural units of at least one of (B1) to (B3), and has 1 to 2 functional groups reactive with (A).

  Of the above (B), from the viewpoint of wettability, (B1) and (B3) are preferable, (B1) is more preferable, and 3-hydroxypropanesulfonic acid (salt) alkylene oxide adduct is particularly preferable. .

[Sulfonic acid (salt) -modified polyolefin (X)]
The sulfonic acid (salt) -modified polyolefin (X) in the present invention is obtained by reacting the above (A) and (B).

  The weight ratio [(A) / (B)] of (A) and (B) when reacting (A) and (B) is a polyolefin resin modifier (X) described later ( From the viewpoint of the compatibility between K) and the polyolefin resin (D) described later and the modification properties of (K), it is preferably 30/70 to 99/1, more preferably 40/60 to 99/2, particularly preferably. 60/40 to 95/5.

  The equivalent ratio [(A) / (B)] of the functional group in (A) and the reactive functional group in (B) in the reaction of (A) and (B) is (K) and From the viewpoint of compatibility with the polyolefin resin (D) described later and the modification property of (K), it is preferably 0.5 to 2.0, more preferably 0.7 to 1.5, and particularly preferably 0.9 to 1.2.

(X) is formed by the reaction of the functional group in (A) with the reactive functional group in (B) to combine (A) and (B). The bond is preferably selected from the group consisting of an ester bond, an imide bond, an amide bond, a urethane bond, a urea bond, a thioester bond, and an epoxy ring-opening bond from the viewpoints of modification characteristics and compatibility with the polyolefin resin (D). At least one bond selected.
Here, the epoxy ring-opening bond includes, for example, bonds represented by the following formulas (2) to (4).
—CH (OH) —CH ₂ —NH— (2)
—CH (OH) —CH ₂ —S— (3)
—CH (OH) —CH ₂ —O—C (═O) — (4)

Specific methods for producing the sulfonic acid (salt) -modified polyolefin (X) include the following methods [1] and [2].
[1] A method in which (A) and (B) are heated and melted, or suspended or dissolved in an appropriate organic solvent (the same as above), and heated and stirred (melting method, suspension method and solution method);
[2] A method in which (A) and (B) are mixed in advance and melt kneaded using an extruder, a Banbury mixer, a kneader or the like (melt kneading method). Among these, the method [1] is preferable from the viewpoint of the reactivity between (A) and (B), and the melting method and the solution method are more preferable.

  The reaction temperature in the melting method may be a temperature at which (A) melts, and is preferably 90 to 180 ° C, more preferably 100 to 150 ° C from the viewpoint of the reactivity between (A) and (B). .

  The reaction temperature in the solution method may be a temperature at which (A) is dissolved in a solvent, and is preferably 50 from the viewpoint of the reactivity between (A) and (B) and the thermal stability of the modifier (K). It is -220 degreeC, More preferably, it is 70-200 degreeC, Most preferably, it is 90-180 degreeC.

The structure of the sulfonic acid (salt) -modified polyolefin (X) can be identified by measuring hydrogen and carbon by ¹ H-NMR and ¹³ C-NMR. These NMR measurements can be performed in a state where a solution dissolved in a mixed solution of heavy toluene and hexachloro-1,3-butadiene is heated to 80 ° C.

  The sulfonic acid (salt) group content of the sulfonic acid (salt) modified polyolefin (X) (unit: mol / kg, hereinafter, only numerical values may be shown) depends on the modification characteristics of the modifier (K) and From the viewpoint of compatibility between the modifier (K) and the polyolefin resin (D), it is preferably 0.1 to 7, more preferably 0.2 to 3.5, and particularly preferably 0.3 to 2. The sulfonic acid (salt) group content can be measured, for example, by the following procedures (i) to (iii). The sulfonic acid (salt) content in Examples described later was in accordance with this method.

(I) 3 g of (X) is heated and melted, followed by pressure molding to produce a circular film having a thickness of 2 mm and a diameter of 37 mm.
(Ii) The sulfur content derived from sulfur oxide (unit: ppm) is measured for the circular film by fluorescent X-ray analysis.
<Measurement conditions>
Equipment: Fully automatic wavelength dispersive X-ray fluorescence spectrometer
["Axios", made by Spectris Co., Ltd.]
X-ray excitation conditions: voltage 50 kV, current 40 mA
Measurement chamber atmosphere: Helium (iii) The sulfonic acid (salt) group content (unit: mol / kg) is calculated according to the following formula.

[Sulphonic acid (salt) group content of (X)]
= [Sulfur content derived from sulfur oxide of (X)] / 32100

[Modifier for polyolefin resin (K)]
The polyolefin resin modifier (K) of the present invention comprises the sulfonic acid (salt) -modified polyolefin (X).

  The polyolefin resin modifier (K) of the present invention comprises the sulfonic acid (salt) -modified polyolefin (X). Since (K) is formed from (A) and (B) as described above, (K) has excellent reforming properties for imparting polarity to polyolefin resin, in particular, wettability to water. .

[Polyolefin resin composition]
The polyolefin resin of this invention contains the said modifier (K) and the below-mentioned polyolefin resin (D).

[Polyolefin resin (D)]
Examples of the polyolefin resin (D) in the present invention include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and Copolymer (random and / or block addition) of ethylene and one or more other α-olefins (C4-12) [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / Vinyl acetate copolymer (EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 95/5 60/40] and the like.

  Mn of (D) is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, from the viewpoint of the mechanical strength of the molded product and the compatibility with (K). The Mw of (D) is preferably 15,000 to 800,000, more preferably 30,000 to 600,000, from the same viewpoint.

As a combination of (D) and (K), there are cases where the structural unit of (D) and the structural unit of the modified polyolefin (A) constituting (K) are the same or similar, and (D) and (K) From the viewpoint of compatibility. For example, when (D) is a propylene unit-containing (ethylene unit-free) (co) polymer, (A) constituting (K) is also a propylene unit-containing (ethylene unit-free) (co) polymer. Some cases are preferred.
The weight ratio [(D) / (K)] between (D) and (K) is preferably 40/60 to 99/1, more preferably 70/30, from the viewpoint of mechanical strength and reforming characteristics. It is -98/2, Most preferably, it is 70 / 30-95 / 5.

  If necessary, a thermoplastic resin other than the polyolefin resin (D) can be used in combination with the resin composition as long as the effects of the present invention are not impaired. Other thermoplastic resins include polyacrylic resins [for example, polymethyl methacrylate, etc.]; polystyrene resins [vinyl group-containing aromatic hydrocarbons alone or vinyl group-containing aromatic hydrocarbons, (meth) acrylic acid esters, (meth ) Copolymers comprising at least one selected from the group consisting of acrylonitrile and butadiene as structural units, such as polystyrene, high impact polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer Polymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin), etc.]]; polyester resin [eg, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane Sandimethylene terephthalate, polybutylene adipate, polyethylene adipate, etc.]; polyamide resin [eg nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, etc.]; Polycarbonate resin [eg polycarbonate, polycarbonate / ABS resin alloy, etc.]; biomass-derived resin [eg polylactic acid, polyhydroxybutyrate, polytrimethylene terephthalate, esterified starch, cellulose acetate, etc.]; polyacetal resin and two or more of these A mixture is mentioned.

The combined amount of the other thermoplastic resins other than (D) is preferably 1 to 30%, more preferably 5 to 5% from the viewpoint of mechanical strength and moldability of the resin composition based on the weight of (D).
25%.

  You may make the polyolefin resin composition of this invention contain the filler (E) which has polarity as needed in the range which does not inhibit the effect of invention. (E) includes metal oxides (alumina, wollastonite, silica, talc, mica, clay, calcined kaolin, etc.), metal hydroxides (aluminum hydroxide, etc.), metal salts (calcium carbonate, calcium silicate, etc.) , Inorganic fiber (carbon fiber, fiber element, α-fiber element, glass fiber, asbestos, etc.), organic fiber (cotton, jute, nylon, acrylic, rayon fiber, etc.), inorganic microballoon (glass, shirasu etc.), organic micro Balloons (phenolic resin, etc.), carbons (carbon black, graphite, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.), wood materials (wood powder, etc.), metal powders (aluminum powder, copper powder, etc.) and these And the like.

  The above (E) can be selected according to the purpose, but from the viewpoint of mechanical strength and heat resistance, preferred are metal oxides, metal salts, inorganic fibers and woody materials, and more preferred are silica and talc. , Calcium carbonate, glass fiber, wood flour.

  The amount of (E) used is preferably 1 to 250%, more preferably from the viewpoint of mechanical strength and moldability of the molded product, based on the total weight of the modifier (K) and the polyolefin resin (D). 5 to 100%, particularly preferably 7 to 50%.

If necessary, the polyolefin resin composition of the present invention can further contain various additives (H) as long as the effects of the present invention are not impaired.
(H) includes colorant (H1), flame retardant (H2), lubricant (H3), antistatic agent (H4), dispersant (H5), antioxidant (H6) and ultraviolet absorber (H7). 1 type (s) or 2 or more types selected from the group which consists of.

  Examples of the colorant (H1) include pigments and dyes. Examples of the pigment include inorganic pigments (alumina white, graphite and the like); organic pigments (azo lake type and the like). Examples of the dye include azo series and anthraquinone series.

  Examples of the flame retardant (H2) include organic flame retardants [nitrogen-containing compounds [salts such as urea compounds and guanidine compounds], sulfur-containing compounds [sulfuric esters, sulfamic acids, and their salts, esters, amides, etc.], silicon-containing compounds Compound [polyorganosiloxane etc.], phosphorus-containing [phosphate ester etc.]]; inorganic flame retardant [antimony trioxide, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, etc.] and the like.

  Examples of the lubricant (G3) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide).

Antistatic agents (H4) include nonionic, cationic, anionic and amphoteric surfactants described below and in US Pat. Nos. 3,929,678 and 4,331,447. .
(1) Nonionic surfactant Alkylene oxide (hereinafter abbreviated as AO) addition type nonionics, for example, active hydrogen atom-containing compound having a hydrophobic group (C8-24 or more) [saturated and unsaturated, higher alcohol (C8-18), higher aliphatic amines (C8-24) and higher fatty acids (C8-24) etc.] (poly) oxyalkylene derivatives (higher fatty acid mono- and di-esters of AO adducts and polyalkylene glycols) A (poly) oxyalkylene derivative of a higher fatty acid (C8-24) ester of a polyhydric alcohol (C3-60) (Tween type nonionics, etc.); a (poly) oxyalkylene derivative of a (alkanol) amide of a higher fatty acid (above) A (poly) oxyalkylene of a polyhydric alcohol (above) alkyl (C3-60) ether Derivatives; and polyoxypropylene polyols [polyoxypropylene derivatives of polyhydric alcohols and polyamines (C2-10) (pluronic and tetronic nonionics)]; polyhydric alcohols (above) type nonionics (for example of polyhydric alcohols) Fatty acid esters, polyhydric alcohol alkyl (C3-60) ethers, and fatty acid alkanolamides); and amine oxide type nonionics [eg (hydroxy) alkyl (C10-18) di (hydroxy) alkyl (C1-3) amine oxide ].

(2) Cationic surfactants Quaternary ammonium salt-type cationix [tetraalkyl ammonium salt (C11-100) alkyl (C8-18) trimethylammonium salt and dialkyl (C8-18) dimethylammonium salt etc.]; trialkyl Benzylammonium salt (C17-80) (lauryldimethylbenzylammonium salt etc.); alkyl (C8-60) pyridinium salt (cetylpyridinium salt etc.); (poly) oxyalkylene (C2-4) trialkylammonium salt (C12-100) ) (Polyoxyethylene lauryl dimethyl ammonium salt, etc.); and acyl (C8-18) aminoalkyl (C2-4) or acyl (C8-18) oxyalkyl (C2-4) tri [(hydroxy) alkyl (C1-4 ]] Ammoni Um salts (sapamine type quaternary ammonium salts) [these salts include, for example, halides (chlorides, bromides, etc.), alkyl sulfates (methosulphate, etc.) and organic acids (below); and amine salt types Cationics: 1-3 primary amines [for example, higher aliphatic amines (C12-60), polyoxyalkylene derivatives of aliphatic amines (methylamine, diethylamine, etc.) [ethylene oxide (hereinafter abbreviated as EO) adducts, etc.], and acyl Aminoalkyl or acyloxyalkyl (above) di (hydroxy) alkyl (above) amine (such as stearoyloxyethyl dihydroxyethylamine, stearamide ethyl diethylamine)], inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.) salt and organic Acid (C2-22) salt.

(3) Anionic surfactant Higher fatty acid (above) salt (such as sodium laurate), ether carboxylic acid [carboxymethylated product of EO (1-10 mol) adduct, etc.], and salts thereof; sulfate salt ( Alkyl and alkyl ether sulfates, etc.), sulfated oils, sulfated fatty acid esters and sulfated olefins; sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid dialkyl ester types, α-olefins (C12-18) Sulfonates, N-acyl-N-methyl taurine (Igepon T type, etc.)], and phosphate ester salts (alkyl, alkyl ethers, alkylphenyl ether phosphates, etc.).

(4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics [amino acid type amphoterics (such as laurylaminopropionic acid (salt)) and betaine type amphoterics (such as alkyldimethylbetaine and alkyldihydroxyethylbetaine)]; sulfuric acid Ester (salt) type amphoterics [sulfuric ester (salt) of laurylamine, hydroxyethyl imidazoline sulfate ester (salt), etc.]; sulfonic acid (salt) type amphoterics [pentadecyl sulfotaurine, imidazoline sulfonic acid ( Salt) etc.], and phosphate ester (salt) type amphoterics etc. [phosphate ester (salt) etc. of glycerol lauryl ester].

  Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; and amine salts and quaternary ammonium salts.

  Examples of the dispersant (H5) include polymers having Mn of 1,000 to 20,000, such as vinyl resin {polyolefin (polyethylene, polypropylene, etc.), modified polyolefin [polyethylene oxide (polyethylene oxide oxidized with ozone, etc., carboxyl group, carbonyl group and And / or those having a hydroxyl group introduced therein), and vinyl resins other than the above polyolefins (polyhalogenated vinyl [polyvinyl chloride, polyvinyl bromide, etc.], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meta ) Acrylic acid, poly (meth) acrylic acid ester [poly (meth) methyl acrylate etc.] and styrene resin [polystyrene, acrylonitrile / styrene (AS) resin etc.] etc .; polyester resin [polyethylene terephthalate etc.], polyamid Examples include resins [6,6-nylon, 12-nylon, etc.], polyether resins [polyethersulfone, etc.], polycarbonate resins [polycondensates of bisphenol A and phosgene, etc.], and block copolymers thereof. .

Antioxidants (H6) include hindered phenol compounds [pt-amylphenol-formaldehyde resin, nordihydroguaiaretic acid (NDGA), 2,6-di-tert-butyl-4-methylphenol (BHT). ), 2-t-butyl-4-methoxyphenol (BHA), 6-t-butyl-2,4, -dimethylphenol (24M6B), 2,6-di-t-butylphenol (26B) and the like];
Sulfur-containing compounds [N, N′-diphenylthiourea, dimyristylthiodipropionate, etc.];
Phosphorus-containing compound [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dioctadecyl-4-hydroxy-3,5-di- t-butylbenzylphosphonate and the like] and the like.

  Examples of the ultraviolet absorber (H7) include salicylate compounds [phenyl salicylate and the like]; benzophenone compounds [2,4-dihydroxybenzophenone and the like]; benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl)- Benzotriazole, etc.].

  The total content of (H) in the polyolefin resin composition is usually 20% or less based on the total weight of the composition, preferably 0.05 to 10 from the viewpoint of functional expression of each (H) and an industrial viewpoint. %, More preferably 0.1 to 5%. The amount of each additive used based on the total weight of the composition is as follows: (H1) is usually 5% or less, preferably 0.1 to 3%; (H2) is usually 8% or less, preferably 1 to 3%; (H3) is usually 8% or less, preferably 1 to 5%; (H4) is usually 8% or less, preferably 1 to 3%; (H5) is usually 1% or less, preferably 0.1 to 0.5%. %; (H6) is usually 2% or less, preferably 0.05 to 0.5%; (H7) is usually 2% or less, preferably 0.05 to 0.5%.

  When the additive is the same and overlaps between (H1) to (H7) above, the amount of each additive exerting the corresponding additive effect is not used as it is, but the effect as the other additive is simultaneously achieved. Considering what is obtained, the usage amount is adjusted according to the purpose of use.

As a production method of the polyolefin resin composition of the present invention,
(1) A method (collective method) in which (D) and (K) and, if necessary, a filler (E) and an additive (H) are mixed together to form a resin composition (collective method);
(2) A master containing a high concentration of (K) by mixing a part of (D), the total amount of (K), and if necessary, a part or all of (E), or a part or all of (H) Includes a method (masterbatch method) in which a batch polyolefin resin composition is once prepared, and then the remaining (D), and if necessary, the remainder of (E) and the remainder of (H) are added and mixed to form a resin composition It is.
The method (2) is preferable from the mixing efficiency of (K).

As a specific mixing method in the manufacturing method of the polyolefin resin composition,
(I) For each component to be mixed, for example, a powder mixer [“Henschel Mixer” [trade name “Henschel Mixer FM150L / B”, Mitsui Mining Co., Ltd., after changing the company name, manufactured by Nippon Coke Industries, Ltd.], “ After mixing with “Nauter Mixer” [trade name “Nauter Mixer DBX3000RX”, manufactured by Hosokawa Micron Co., Ltd.], “Banbury Mixer” [trade name “MIXTRON BB-16MIXER”, manufactured by Kobe Steel, Ltd.], etc.] A method of kneading usually at 120 to 220 ° C. for 2 to 30 minutes using a melt kneader [batch kneader, continuous kneader (single screw kneader, biaxial kneader, etc.)];
(Ii) A method of directly kneading the components to be mixed under the same conditions using the same melt-kneading apparatus as described above without mixing powders in advance.
Among these methods, the method (i) is preferable from the viewpoint of mixing efficiency.

  Since the polyolefin resin modifier (K) of the present invention has excellent affinity with materials having greatly different polarities, the (K) or the polyolefin resin composition containing the (K) is a polyolefin resin or the like. It has a feature that it has excellent affinity for both nonpolar plastics and highly polar plastics such as polyurethane. Therefore, in the adhesion between plastics having different polarities (when one is a base material and the other is a coating film, etc.), the modifier (K) of the present invention or the polyolefin resin composition containing the (K) is Also, it can be applied as a primer for plastic molded products.

  Further, by molding the resin composition containing the filler (E), a molded product having excellent mechanical strength (such as flexural modulus) and heat resistance (such as deflection temperature under load) can be obtained. it can.

[Molded articles and molded articles]
The molded product of the present invention is obtained by molding the above resin composition. Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like. Molding can be performed by any method that incorporates means such as layer molding, multilayer molding, and foam molding.

  A molded product formed by molding the resin composition of the present invention has excellent mechanical strength and good paintability and printability, and a molded article can be obtained by coating and / or printing the molded product. can get. Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating. Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

  In addition, as a method of printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing , Screen printing, pad printing, dry offset printing, offset printing, and the like. As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

  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”.

[Production of polyolefin (a0)]
Production Example 1
In a reaction vessel equipped with a nitrogen introduction tube, an exhaust gas distillation tube, a stirrer, and a cooling tube, a polyolefin having a structural unit of 98 mol% propylene and 2 mol% ethylene [trade name “Sun Allomer PZA20A”, manufactured by Sun Allomer Co., Ltd., Mw 200,000, 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, and subjected to thermal degradation at 360 ° C. for 40 minutes with stirring to obtain polyolefin (a0-1). . (A0-1) had Mw 41,000 and the number of double bonds per 1,000 carbon atoms was 2.1.

Production Example 2
In Production Example 1, a polyolefin (a0-2) was obtained in the same manner as in Production Example 1 except that the heat degradation time was changed from 40 minutes to 80 minutes. (A0-2) had Mw of 7,000 and the number of double bonds per 1,000 carbon atoms was 12.3.

Production Example 3
In Production Example 1, a polyolefin (a0-3) was obtained in the same manner as in Production Example 1 except that the heat degradation time was changed from 40 minutes to 65 minutes. As for (a0-3), Mw27,000 and the number of double bonds per 1,000 carbon atoms were 4.1.

[Production of Modified Polyolefin (A)]
Production Example 4
In a reaction vessel similar to Production Example 1, 95 parts of (a0-1), 5 parts of maleic anhydride and 100 parts of xylene were charged, heated to 130 ° C. in a nitrogen atmosphere, and uniformly dissolved. A solution prepared by dissolving 0.5 part of dicumyl peroxide in 10 parts of xylene was added dropwise thereto, and then the temperature was raised to xylene reflux temperature and stirring was continued for 3 hours. Thereafter, xylene and unreacted maleic anhydride are distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain a modified polyolefin (A-1) having 4 acid anhydride groups per molecule. It was. The Mw of (A-1) was 42,000.

Production Example 5
In a reaction vessel similar to Production Example 1, 90 parts of (a0-1) and 30 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. and melted in a nitrogen atmosphere. Next, 5 parts of methacrylic acid and 0.5 part of dicumyl peroxide dissolved in 10 parts of xylene were added dropwise, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-2) having two carboxyl groups per molecule. Mw of (A-2) was 41,500.

Production Example 6
In the same reaction vessel as in Production Example 1, 30 parts of (a0-2) and 100 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. and melted in a nitrogen atmosphere. Next, 70 parts of methacrylic acid and 0.5 part of dicumyl peroxide dissolved in 10 parts of xylene were dropped, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-3) having 23 carboxyl groups per molecule. Mw of (A-3) was 15,000.

Production Example 7
In a reaction vessel similar to Production Example 1, 95 parts of (a0-1) and 30 parts of xylene were charged into another reaction vessel equipped with a cooling tube, purged with nitrogen, heated to 150 ° C. in a nitrogen atmosphere, and melted. I let you. Next, 5 parts of aminoethyl methacrylate and 0.5 part of dicumyl peroxide dissolved in 10 parts of xylene were added dropwise, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-4) having three amino groups per molecule. Mw of (A-4) was 42,000.

Production Example 8
In the same reaction vessel as in Production Example 1, 85 parts of (a0-3) and 30 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. and melted in a nitrogen atmosphere. Next, 15 parts of glycidyl methacrylate and 0.5 part of dicumyl peroxide dissolved in 10 parts of xylene were added dropwise, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-5) having 4 epoxy groups per molecule. The Mw of (A-5) was 28,500.

Production Example 9
In a reaction vessel similar to Production Example 1, 97 parts of (a0-1) and 30 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. and melted in a nitrogen atmosphere. Next, 3 parts of 2-mercaptoethyl methacrylate and 0.5 part of dicumyl peroxide dissolved in 10 parts of xylene were added dropwise, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-6) having two thiol groups per molecule. Mw of (A-6) was 43,000.

Production Example 10
In a reaction vessel similar to Production Example 1, 99 parts of (a0-1) and 30 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. and melted in a nitrogen atmosphere. Next, 0.3 part of dicumyl peroxide dissolved in 1 part of 2-hydroxyethyl methacrylate and 10 parts of xylene was added dropwise, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-7) having one hydroxyl group per molecule. The Mw of (A-7) was 41,500.

Production Example 11
In a reaction vessel similar to Production Example 1, 97 parts of (A-1) and 40 parts of xylene were charged and purged with nitrogen, and then heated to 120 ° C. and melted in a nitrogen atmosphere. Next, 6 parts of monoethanolamine was added and stirring was continued at 120 ° C. for 3 hours. Thereafter, unreacted monoethanolamine and xylene were distilled off under reduced pressure to obtain a modified polyolefin (A-8) having four hydroxyl groups per molecule. The Mw of (A-8) was 42,500.

Production Example 12
In a reaction vessel similar to Production Example 1, 95 parts of (a0-1) and 30 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. and melted in a nitrogen atmosphere. Next, 0.3 part of dicumyl peroxide dissolved in 5 parts of 2-isocyanatoethyl methacrylate and 10 parts of xylene was added dropwise, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-9) having two isocyanate groups per molecule. The Mw of (A-9) was 42,000.

Production Example 13
In the same reaction vessel as in Production Example 1, 85 parts of (a0-3) and 30 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. and melted in a nitrogen atmosphere. Next, 15 parts of maleic anhydride and 0.3 part of dicumyl peroxide dissolved in 10 parts of xylene were added dropwise, and stirring was continued at 150 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain a modified polyolefin (A-10) having 8 acid anhydride groups per molecule. Mw of (A-10) was 30,000.

Production Example 14
In a reaction vessel similar to Production Example 1, 92 parts of (A-10) and 40 parts of xylene were charged and purged with nitrogen, and then heated to 120 ° C. and melted in a nitrogen atmosphere. Next, 16 parts of monoethanolamine was added and stirring was continued at 120 ° C. for 3 hours. Thereafter, unreacted monoethanolamine and xylene were distilled off under reduced pressure to obtain a modified polyolefin (A-11) having 16 hydroxyl groups per molecule. Mw of (A-11) was 32,000.

Production Example 15
After charging 95 parts of (a0-2), 6 parts of maleic anhydride and 30 parts of xylene into the same reaction vessel as in Production Example 1, and substituting with nitrogen, the mixture was heated to 210 ° C. and melted in a nitrogen atmosphere. The stirring was continued at 210 ° C. for 10 hours. Thereafter, unreacted maleic anhydride and xylene were distilled off under reduced pressure to obtain a modified polyolefin (A-12) having two acid anhydrides per molecule. Mw of (A-12) was 8,000.

[Production of sulfonic acid (salt) group-containing compound]
Production Example 15
In the same reaction vessel as in Production Example 1, 24 parts of sodium sulfite, 30 parts of sodium persulfate, 50 parts of ion-exchanged water, allyl alcohol ethylene oxide adduct (EO 8 mol adduct) [trade name “NB-30” Sanyo Chemical Industries Made by Co., Ltd.] 100 parts were charged, heated with a mantle heater while nitrogen was passed through the gas phase, and reacted at 70 ° C. for 3 hours with stirring. Subsequently, after stirring under reduced pressure to remove water, the reaction vessel was cooled to 30 ° C., and 10 parts of 35% aqueous hydrogen peroxide was added. Solid-liquid separation was performed using a centrifuge, and the liquid phase was transferred to the same reaction vessel as in Production Example 1. Next, water was removed while stirring under reduced pressure to obtain 3-hydroxypropanesulfonic acid sodium salt alkylene oxide adduct (EO 8 mol adduct) (B1-1).

Production Example 16
A reaction vessel similar to Production Example 1 was charged with 46.9 parts of isophoronediamine, 20.3 parts of isophthalic acid, and 32.8 parts of monosodium 3-sulfoisophthalic acid, and a mantle heater ventilating nitrogen in the gas phase part. The mixture was reacted at 160 ° C. for 5 hours while distilling off water under stirring and stirring under reduced pressure to obtain a sulfonic acid (salt) group-containing compound (B4-1) having two amino groups.

Production Example 17
A reaction vessel similar to Production Example 1 is charged with 43.6 parts of isophoronediamine, 17 parts of isophthalic acid, 34.3 parts of 3-sulfoisophthalic acid monosodium salt, and 5.1 parts of dodecanoic acid, and nitrogen is added to the gas phase part. Heating with a mantle heater with aeration, stirring, distilling off water under reduced pressure, reacting at 160 ° C. for 5 hours, sulfonic acid (salt) group-containing compound having one amino group (B4-2) Got.

Production Example 18
A reaction vessel similar to Production Example 1 was charged with 21.9 parts of ethylene glycol, 22 parts of isophthalic acid, 47.3 parts of monosodium 3-sulfoisophthalic acid, and 8.8 parts of dodecanoic acid, and nitrogen was added to the gas phase part. Heating with a mantle heater with aeration, stirring, distilling off water under reduced pressure, reacting at 200 ° C. for 8 hours, sulfonic acid (salt) group-containing compound having one hydroxyl group (B4-3) Got.

Production Example 19
A reaction vessel similar to Production Example 1 was charged with 18 parts of ethylene glycol, 5.3 parts of lauryl alcohol, 14.5 parts of isophthalic acid, and 62.2 parts of 3-sulfoisophthalic acid monosodium salt, and nitrogen was added to the gas phase part. Heating with a mantle heater while aeration, stirring, distilling off water under reduced pressure, reacting at 200 ° C. for 8 hours, sulfonic acid (salt) group-containing compound (B4-4) having one carboxyl group Got.

[Resin modifier for polyolefin]
Example 1
In a reaction vessel similar to Production Example 1, 88 parts of (A-1) and 12 parts of (B1-1) were charged and purged with nitrogen, then heated to 180 ° C. in a nitrogen atmosphere and melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-1) containing sulfonic acid (salt) -modified polyolefin (X-1).

Example 2
A reaction vessel similar to Production Example 1 was charged with 94 parts of (A-1) and 6 parts of 3-hydroxypropanesulfonic acid [manufactured by Tokyo Chemical Industry Co., Ltd.] (B1-2). Then, the mixture was heated to 180 ° C. and melted to continue stirring for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-2) containing sulfonic acid (salt) -modified polyolefin (X-2).

Example 3
In a reaction vessel similar to Production Example 1, 95 parts of (A-1) and 5 parts of N-methyltaurine sodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B2-1) were charged, and the atmosphere was replaced with nitrogen. Then, the mixture was heated to 180 ° C. and melted to continue stirring for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-3) containing sulfonic acid (salt) -modified polyolefin (X-3).

Example 4
In a reaction vessel similar to Production Example 1, 93 parts of (A-2) and 7 parts of (B1-1) were charged, purged with nitrogen, heated to 180 ° C. in a nitrogen atmosphere, melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-4) containing sulfonic acid (salt) -modified polyolefin (X-4).

Example 5
In a reaction vessel similar to Production Example 1, 97 parts of (A-2) and 3 parts of 3-hydroxypropanesulfonic acid [manufactured by Tokyo Chemical Industry Co., Ltd.] (B1-2) were charged, and the atmosphere was replaced with nitrogen. Then, the mixture was heated to 180 ° C. and melted to continue stirring for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-5) containing sulfonic acid (salt) -modified polyolefin (X-5).

Example 6
In a reaction vessel similar to Production Example 1, 97 parts of (A-2) and 3 parts of N-methyltaurine sodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B2-1) were substituted, and the atmosphere was replaced with nitrogen. The mixture was heated to 180 ° C. and melted and stirred for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-6) containing sulfonic acid (salt) -modified polyolefin (X-6).

Example 7
In a reaction vessel similar to Production Example 1, 31 parts of (A-3) and 69 parts of (B1-1) were charged and purged with nitrogen, then heated to 180 ° C. in a nitrogen atmosphere and melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-7) containing sulfonic acid (salt) -modified polyolefin (X-7).

Example 8
In a reaction vessel similar to Production Example 1, 50 parts of (A-3) and 50 parts of 3-hydroxypropanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (B1-2) were charged and purged with nitrogen. The mixture was heated to 180 ° C. under an atmosphere and melted and stirred for 1 hour, then stirred for 3 hours under reduced pressure, and modified for polyolefin resin containing sulfonic acid (salt) -modified polyolefin (X-8). A quality agent (K-8) was obtained.

Example 9
A reaction vessel similar to Production Example 1 was charged with 53 parts of (A-3) and 47 parts of N-methyltaurine sodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B2-1), and the atmosphere was replaced with nitrogen. Then, the mixture was heated to 180 ° C. and melted to continue stirring for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-9) containing sulfonic acid (salt) -modified polyolefin (X-9).

Example 10
After charging 93 parts of (A-4) and 7 parts of 3-sulfobenzoic acid monosodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B3-1) in a reaction container similar to Production Example 1, and substituting with nitrogen, Under a nitrogen atmosphere, the temperature was raised to 180 ° C. and the mixture was melted and stirred for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-10) containing sulfonic acid (salt) -modified polyolefin (X-10).

Example 11
In a reaction container similar to Production Example 1, 87 parts of (A-5) and 13 parts of 3-sulfobenzoic acid monosodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B3-1) were charged, and the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, the temperature was raised to 180 ° C. and the mixture was melted and stirred for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-11) containing sulfonic acid (salt) -modified polyolefin (X-11).

Example 12
In the same reaction vessel as in Production Example 1, 95 parts of (A-6) and 5 parts of 3-sulfobenzoic acid monosodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B3-1) were charged, and the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, the temperature was raised to 180 ° C. and the mixture was melted and stirred for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-12) containing sulfonic acid (salt) -modified polyolefin (X-12).

Example 13
In a reaction container similar to Production Example 1, 97 parts of (A-7) and 3 parts of 3-sulfobenzoic acid monosodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B3-1) were charged, and the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, the temperature was raised to 180 ° C. and the mixture was melted and stirred for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-13) containing sulfonic acid (salt) -modified polyolefin (X-13).

Example 14
In a reaction container similar to Production Example 1, 91 parts of (A-8) and 9 parts of 3-sulfobenzoic acid monosodium salt (manufactured by Tokyo Chemical Industry Co., Ltd.) (B3-1) were charged, and the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, the temperature was raised to 180 ° C. and the mixture was melted and stirred for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-14) containing sulfonic acid (salt) -modified polyolefin (X-14).

Example 15
In a reaction vessel similar to Production Example 1, 93 parts of (A-9) and 7 parts of (B1-1) were charged and purged with nitrogen, then heated to 180 ° C. in a nitrogen atmosphere, melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-15) containing sulfonic acid (salt) -modified polyolefin (X-15).

Example 16
In a reaction vessel similar to Production Example 1, 65 parts of (A-11) and 35 parts of 3-sulfobenzoic acid monosodium salt [manufactured by Tokyo Chemical Industry Co., Ltd.] (B3-1) were charged, and the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, the temperature was raised to 180 ° C. and the mixture was melted and stirred for 1 hour. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-16) containing sulfonic acid (salt) -modified polyolefin (X-16).

Example 17
In a reaction vessel similar to Production Example 1, 40 parts of (A-12) and 60 parts of (B4-1) were charged and purged with nitrogen, then heated to 180 ° C. in a nitrogen atmosphere and melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-17) containing sulfonic acid (salt) -modified polyolefin (X-17).

Example 18
In the same reaction vessel as in Production Example 1, 22 parts of (A-12) and 78 parts of (B4-2) were charged and purged with nitrogen, then heated to 180 ° C. in a nitrogen atmosphere and melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-18) containing sulfonic acid (salt) -modified polyolefin (X-18).

Example 19
In a reaction vessel similar to Production Example 1, 34 parts of (A-12) and 66 parts of (B4-2) were charged and purged with nitrogen, then heated to 180 ° C. in a nitrogen atmosphere and melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-19) containing sulfonic acid (salt) -modified polyolefin (X-19).

Example 20
In a reaction vessel similar to Production Example 1, 23 parts of (A-12) and 77 parts of (B4-2) were charged and purged with nitrogen, then heated to 180 ° C. in a nitrogen atmosphere and melted, and stirred for 1 hour. Continued. Next, the mixture was stirred for 3 hours under reduced pressure to obtain a polyolefin resin modifier (K-20) containing sulfonic acid (salt) -modified polyolefin (X-20).

  The results of Examples 1 to 20 are shown in Table 1.

[Polyolefin resin composition, molded product]
Examples 21-47, Comparative Examples 1-4
Commercially available polyolefin resin (D-1) [trade name “Sun Allomer PM970A”, polypropylene, manufactured by Sun Allomer Co., Ltd., and so on. ], Polyolefin resin modifiers (K-1) to (K-16), and modified polyolefin (A-1), respectively, in a twin screw extruder with a vent according to the blending composition of Table 2 at 190 ° C., 100 rpm, The resin composition was obtained by melt-kneading under the condition of a residence time of 5 minutes. The resin composition was molded using an injection molding machine [model number “PS40 ESASE”, manufactured by Nissei Plastic Industry Co., Ltd.] under conditions of a resin temperature of 190 ° C., an injection speed of 50 mm / s, and a mold temperature of 40 ° C. A 4 mm flat sheet-like molded product was obtained, and test plates for performance evaluation described later were prepared. Each test plate was evaluated for performance. The results are shown in Table 2.

The performance evaluation was performed according to the following method.
<Evaluation method>
1. Impact resistance (Unit: J / m)
Izod impact values were measured according to ASTM D256.
2. Tensile modulus (unit: MPa)
The measurement was performed according to JIS K7161.
3. Wettability (Unit: °)
The water contact angle was measured according to JIS R3257. A smaller water contact angle indicates better wettability.
4). Persistence of wettability (unit: °)
The test plate was immersed in water and the surface was washed with a cotton cloth, followed by drying under reduced pressure (1 kPa, 80 ° C., 1 hour). This test piece was temperature-controlled (23 ° C., 50 RH%, 24 hours), and the above 3. Similarly, the water contact angle was measured.

  From the results of Table 2, the polyolefin resin modifier (K) of the present invention has a wettability (polarity) with respect to water, in particular with respect to water, without compromising the mechanical strength of the polyolefin resin as compared with the comparative one. It can be seen that it is excellent in the reforming property that imparts the durability of the property. Moreover, it is clear that the molded article of the polyolefin resin composition containing the (K) is excellent in water wettability and mechanical strength.

  The polyolefin resin modifier (K) of the present invention imparts wettability to water or compatibility with other resins having different polarities without reducing the mechanical strength of the molded product. The molded article formed by molding the polyolefin resin composition containing the modifier (K) is excellent in water wettability, affinity with other resins having different polarities, and mechanical strength. Excellent balance. Therefore, the modifier (K) is used as a polyolefin resin modifier, the resin composition containing (K) or (K) is used as a primer for a plastic molded article, and the composition is molded. As molded articles and molded articles, the present invention can be applied to a wide range of fields such as for electric and electronic equipment, for packaging materials, for conveying materials, for household materials and for building materials. Here, the living materials include, for example, furniture (chairs, desks, hangers, etc.), hobby goods (sports equipment, etc.), gardening goods (planters, etc.), daily goods [tableware, toys, stationery, toiletries, sanitary materials (paper diapers). The building material is not limited as long as it is a material used for construction of a house or the like. For example, various doors such as entrances and rooms, inner and outer wall materials, ceiling materials, roofs, etc. Materials, heat insulation and heat shielding materials.

Claims (10)

  Modified polyolefin (A) having at least one functional group selected from the group consisting of an acid anhydride group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, amino group and thiol group, and a functional group reactive with (A) A polyolefin resin modifier (K) comprising a sulfonic acid (salt) -modified polyolefin (X) formed from a sulfonic acid (salt) group-containing compound (B) having a group.   The modifying functional group according to claim 1, wherein the reactive functional group of (B) is at least one selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group.   Claims where (A) and (B) are bonded via at least one bond selected from the group consisting of an ester bond, an imide bond, an amide bond, a urethane bond, a urea bond, a thioester bond and an epoxy ring-opening bond. Item 3. A modifier according to item 1 or 2.   The weight ratio [(A) / (B)] of (A) and (B) is 30/70 to 99/1, The modifier according to any one of claims 1 to 3.   The modifier according to any one of claims 1 to 4, wherein the content of the sulfonic acid (salt) group in (X) is 0.1 to 7 mol / kg.   A polyolefin resin composition comprising the modifier (K) according to any one of claims 1 to 5 and a polyolefin resin (D).   The composition according to claim 6, wherein the weight ratio [(D) / (K)] of (D) and (K) is 40/60 to 99/1.   A molded article formed by molding the composition according to claim 6 or 7.   A molded article obtained by coating and / or printing the molded article according to claim 8.   A modified polyolefin (A) having at least one functional group selected from the group consisting of an acid anhydride group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, an amino group and a thiol group; and a functional group reactive with (A) A method for producing a polyolefin resin modifier (K) containing a sulfonic acid (salt) -modified polyolefin (X), wherein the sulfonic acid (salt) group-containing compound (B) having a group is reacted.