JP6279844B2 - Process for producing modified polyolefin - Google Patents

Description

  The present invention relates to a method for producing a modified polyolefin. More specifically, the present invention relates to a method for producing a modified polyolefin in which a polyolefin, an unsaturated (poly) carboxylic acid (anhydride), and an ethylenically unsaturated monomer are reacted in the presence of a radical initiator.

  Modified polyolefins are widely used as resin surface modifiers, dispersants, compatibilizers, and the like. As a method for producing them, low molecular weight polyolefins obtained by polymerization of olefin monomers or polymers obtained by polymerization of olefin monomers can be used. A method of graft polymerizing an unsaturated carboxylic acid to a low molecular weight polyolefin obtained by thermal degradation of a molecular weight polyolefin in the presence of a radical initiator (see, for example, Patent Document 1), in the presence of a radical initiator to a high molecular weight polyolefin A method is known in which unsaturated carboxylic acid is added to cause thermal degradation of high-molecular-weight polyolefin and graft polymerization of unsaturated carboxylic acid to polyolefin simultaneously (for example, see Patent Document 2).

JP 2005-194507 A JP-A-6-287401

However, the above-mentioned method for producing a modified polyolefin is a graft polymerization of unsaturated carboxylic acid by a hydrogen abstraction reaction with a radical initiator in the polyolefin chain. Since there is a large amount of free unsaturated carboxylic acid that does not remain, there is a problem that the effect of the odor of the resulting modified polyolefin and the aforementioned modifier cannot be expected. Further, since a large amount of free unsaturated carboxylic acid is contained, there is a problem that mechanical properties such as a molded article made of a polyolefin resin composition containing the modified polyolefin are lowered, and improvement has been desired.
An object of the present invention is to provide a method for producing a modified polyolefin having a high graft ratio of unsaturated carboxylic acid to polyolefin and a small amount of free unsaturated carboxylic acid.

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 relates to a modified polyolefin in which a polyolefin (A), an unsaturated (poly) carboxylic acid (anhydride) (B), and an ethylenically unsaturated monomer (C) are reacted in the presence of a radical initiator (D). In the production method, the following formulas (1) and (2) are satisfied, (A) has 0.1 to 20 double bonds per 1,000 carbon atoms, and (C) has 6 carbon atoms. A process for producing a modified polyolefin (X), which is a linear or branched α-olefin of 36 to 36 .

0 <r _b × r _c <1.0 (1)

0 <r _c <1.5 (2)

[In the formulas (1) and (2), r _b is the reactivity ratio of (B) defined by r _b = k _bb / k _bc , and r _c is defined by r _c = k _cc / k _cb ( C) reactivity ratio; k _mn (m and n are each b or c) is a growth reaction rate constant, m is a monomer species at the growth end active site, and n is a monomer species to be added to the active site. Represent each. That is, k _bc when m is b and n is c represents a growth reaction rate constant when the monomer (C) is added to the monomer (B) at the active site, and m and n are k _{mn of} other combinations. Represents a growth reaction rate constant defined similarly. ]

The method for producing the modified polyolefin of the present invention, the modifier comprising the modified polyolefin produced by the production method, and the molded product obtained by molding the polyolefin resin composition containing the modifier are as follows: There is an effect.
(1) The modified polyolefin produced by the production method has a high copolymerization ratio of unsaturated carboxylic acid.
(2) The modifier imparts an excellent modification effect (surface modification effect, water wettability) to the molded article of the polyolefin resin composition without impairing the original mechanical strength.

[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 moldability of the polyolefin resin composition and the molecular end of (A) and From the viewpoint of the amount of double bonds in the molecular chain, preferably 30/70 to 99/1, more preferably 50/50 to 95/5), etc .; propylene unit-containing (ethylene unit-free) (co) polymer For example, a copolymer of polypropylene, propylene and an unsaturated monomer of C4-30 (same as above) (weight ratio is the same as above); ethylene / propylene copolymer (weight ratio is polyolefin resin group) From the viewpoint of the moldability of the product and the amount of double bonds in the molecular ends and / or molecular chains of (A), 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, an ethylene / propylene copolymer are preferable from the viewpoint of polymerizability with an unsaturated (poly) carboxylic acid (anhydride) (B) and an ethylenically unsaturated monomer (C) described later. A propylene / C4-30 unsaturated monomer copolymer, an ethylene / propylene copolymer, and a propylene / C4-30 unsaturated monomer copolymer are more preferable.

  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 from 800 to 45,000, more preferably from 1,000 to 40,000, from the viewpoint of the mechanical strength of the molded product described later and the productivity of the resin modifier (K) described later.

The measurement conditions of Mn by GPC in the present invention are as follows.
Apparatus: High-temperature gel permeation chromatograph
["Alliance GPC V2000",
Waters Co., Ltd.]
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 double bond in the molecular terminal and / or molecular chain from the viewpoint of copolymerization with an unsaturated (poly) carboxylic acid (anhydride) (B) and an ethylenically unsaturated monomer (C) described later. It is preferable to have.
The number of double bonds in the molecular end and / or molecular chain per 1,000 carbons (also referred to as 1,000 carbon atoms) of (A) is as follows: (A), (B) and (C) From the viewpoint of copolymerization and productivity of the modified polyolefin (X) defined later, 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, the thermal degradation method includes the polyolefin (A0) under nitrogen aeration and (1) in the absence of organic peroxide, usually at 300 to 450 ° C. for 0.5 to 10 hours. And (2) a method of thermally degrading usually at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide.
Of these, preferred from the viewpoint of the copolymerizability between (A) and (B) and (C) obtained are those having a larger number of double bonds in the molecular terminal and / or molecular chain ( This is the method 1).

  Of these production methods of (A), those having a larger number of double bonds in the molecular terminals and / or molecular chains can be easily obtained, and the copolymerization of (A), (B) and (C) is easy. From the viewpoint of being, it is preferable to use a degradation method, and more preferable to use a thermal degradation method.

[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) Tendenedicarboxylic acid, methyltetrahydrophthalic acid, and their anhydrides) and the like. (B) may be used alone or in combination of two or more.
Of the above (B), an unsaturated dicarboxylic anhydride is preferred from the viewpoint of copolymerization with the ethylenically unsaturated monomer (C) described later, and maleic anhydride is more preferred. .

[Ethylenically unsaturated monomer (C)]
The ethylenically unsaturated monomer in the present invention includes the following (1) unsaturated aliphatic hydrocarbon, (2) aromatic ring-containing vinyl compound, (3) unsaturated carboxylic acid ester and the like.
(1) Aliphatic unsaturated hydrocarbon Other than C2-30 alkene, C6 to 36 (more preferably C8 to 30) linear α-olefin and branched α-olefin having (A) And other C4-30 unsaturated monomers having a copolymerizability with olefins (such as butadiene).
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.

(2) Aromatic ring-containing vinyl compound C8-20, styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, vinyl Naphthalene and a mixture of two or more thereof may be mentioned.

(3) Unsaturated carboxylic acid ester C4-20, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl ( And (meth) acrylate, dicyclopentadienyl (meth) acrylate, and a mixture of two or more thereof.
Among the above (C), from the viewpoint of the modification effect of the later-described modifier (K) containing the copolymerizable and modified polyolefin (X) defined later with (B), Aliphatic unsaturated hydrocarbons, more preferably C6-36 (particularly preferably C8-30), linear α-olefins and branched α-olefins.

[Radical initiator (D)]
The modified polyolefin (X) in the present invention is obtained by copolymerizing the above (A), (B), (C) in the presence of the radical initiator (D).
Examples of (D) include azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), etc.], peroxides [monofunctional (in the molecule (Having one peroxide group) (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, diallylperoxydicarbonate, etc.]] and the like.
Among these, (A), (B), or (A), (B), (C) from the viewpoint of polymerizability, that is, (A) is trunk, (B) or (B) and (C), which will be described later. From the viewpoint of the formation of a graft copolymer having a (co) polymer as a branch, a peroxide is preferable, a monofunctional peroxide is more preferable, and a di-t-butyl peroxide is particularly preferable. , 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%.

[Production Method of Modified Polyolefin (X)]

The specific production method (X) includes the following methods [1] and [2].
[1] (A), (B) and (C) are mixed with a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbon (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 (D) [or a solution in which (D) is dissolved in an appropriate organic solvent (the same as above)], and a chain transfer agent (t) described below, if necessary, polymerization Method of adding the inhibitor (f) and stirring with heating (solution method);
[2] A method in which (A), (B), (C), (D), and (t), (f) as necessary are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like ( Melting method).

  The reaction temperature in the solution method may be a temperature at which (A) is dissolved in an organic solvent, and is preferably 50 to 220 ° C. from the viewpoint of copolymerization and productivity of (A), (B) and (C). More preferably, it is 110-210 degreeC, Most preferably, it is 120-180 degreeC.

  The reaction temperature in the melting method may be a temperature at which (A) melts, and is preferably 120 from the viewpoints of the copolymerizability of (A), (B) and (C) and the decomposition temperature of the reaction product. It is -260 degreeC, More preferably, it is 130-240 degreeC.

Examples of the chain transfer agent (t) include: alcohol (C1-24, such as methanol, ethanol, 1-propanol, 2-butanol, allyl alcohol); thiol (C1-24, such as ethanethiol, propanethiol, 1- And 2-butanethiol, 1-octanethiol); aldehydes (C2-18, such as 1- and 2-butyraldehyde, 1-pentylaldehyde); phenols (C6-36, such as phenol, o-, m- and p-) Cresol); amines (C3-24, such as diethylmethylamine, triethylamine, diphenylamine); disulfides (C2-24, such as diethyldisulfide, di-1-propyldisulfide).
The amount of (t) used is usually 30% or less based on the total weight of (A), (B) and (C), the copolymerizability of (A), (B) and (C) and (X) From the viewpoint of productivity, 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 used of (f) is usually 5% or less based on the total weight of (A), (B) and (C), the stability of productivity (A), (B) and (C) and (A) From the viewpoint of the reactivity of (B) and (C), it is preferably 0.01 to 0.5%.

  The Mn of the modified polyolefin (X) is preferably 1,500 to 70,000, more preferably 2,000 to 60, from the viewpoint of mechanical properties and moldability of a molded product (hereinafter sometimes referred to simply as a molded product) described later. 1,000, particularly preferably 2,500 to 50,000.

The acid value of (X) is preferably 50 to 250 mgKOH / g (only numerical values are shown below), more preferably from the viewpoint of the wettability of the molded product and the compatibility between (X) and the polyolefin resin (E) described later. Is 65-200. 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.

The production method of the modified polyolefin (X) of the present invention satisfies the following formulas (1) and (2), and preferably satisfies the following formulas (3) and (4).

0 <r _b × r _c <1.0 (1)

0 <r _c <1.5 (2)

r _b × r _c <0.01 (3)

0 <r _c <1.0 (4)

In the formulas (1) to (4), r _b is the reactivity ratio of (B) defined by r _b = k _bb / k _bc , and r _c is defined by r _c = k _cc / k _cb (C reactivity ratios); k _mn (m, n represents the b or c, respectively) is the growth rate constant, m is the monomer species growing end active sites, n represents the monomer species to be added to the active point, respectively Represent. That is, k _bc when m is b and n is c represents a growth reaction rate constant when the monomer (C) is added to the monomer (B) at the active site, and m and n are k _{mn of} other combinations. Represents a growth reaction rate constant defined similarly.
More specifically, the above _kmn is represented by the following reaction formula.

k _bb
M _b ^* + M _b → M _b ^*
k _bc
M _b ^* + M _c → M _c ^*
k _cb
M _c ^* + M _b → M _b ^*
k _cc
M _c ^* + M _c → M _c ^*

Here, when considering the copolymerization including two types of monomers (M _b and M _c ), M _b ^* and M _c ^* represent growing polymer chains having M _b and M _c as terminal monomer units, respectively. .
The value of r _b, r _c is the value calculated Q according, from e value in POLYMER HANDBOOK (J.Brandrup, E.H.Immergut, E.A.Grulke ). The Q and e values are parameters that characterize the reactivity of the monomer, and are related to the resonance factor (resonance stability of radicals generated by the addition of the monomer) and polar factor (charge amount of the double bond of the monomer), respectively. The value to be The greater the Q value, the greater the copolymerization reactivity of the monomer, and the combination of monomers with a large difference in e value becomes more alternating. Specifically, it can be obtained from the following equation.

_{r b = (Q b / Q} c) × EXP (-e b × (e b -e c))

r _c = (Q _c / Q _b ) × EXP (−e _c × (e _c −e _b ))

Here, Q _b value, Q _c value, e _b value, e _c values each of Q value of the monomers (M _b and M _c), representing an e value.

In the formula (1), as r _b × r _c is close to zero less than 1, the better the alternating copolymerization of (B) (C), and alternating copolymer resistance deteriorates in 1 or more. Further, in the formula (2), the r _c is 1.5 or more increases the content of (C) in the copolymer [modified polyolefin (X)], the wettability of the molded article to be described later is deteriorated.
Here, as a combination of the monomers (B) and (C) satisfying the formulas (1) and (2), for example, maleic anhydride / aliphatic unsaturated hydrocarbon, maleic anhydride / styrene, and acrylic acid / In view of copolymerization with (A), maleic anhydride / aliphatic unsaturated hydrocarbon is preferable, and maleic anhydride and C6-36 are preferably used. A chain α-olefin and a branched chain α-olefin.

[Modified polyolefin (X)]
The modified polyolefin (X) in the present invention comprises the polyolefin (A), unsaturated (poly) carboxylic acid (anhydride) (B) and ethylenically unsaturated monomer (C) as structural units.

  The weight ratio [(A) / (B)] of (A) and (B) in (X) is preferably 30/70 to 92/8, more preferably from the viewpoint of mechanical strength and wettability of the molded product. 35/65 to 80/20; (A) and (C) weight ratio [(A) / (C)] is preferably 23/77 to 94 / from the viewpoint of mechanical strength and wettability of the molded product. 6, more preferably 30/70 to 85/15; the weight ratio of (A) to the sum of (B) and (C) [(A) / [(B) + (C)]] From the viewpoint of the mechanical strength and wettability, preferably 20/80 to 85/15, more preferably 30/70 to 80/20; and the weight ratio of (B) to (C) [(B) / (C) ] Is preferably 11/89 to 90/10, more preferably 15/85 to 80, from the viewpoint of wettability and mechanical strength of the molded product. 20.

  The content of each component based on the total weight of (A), (B), and (C) is as follows. (A) is the productivity of the resin modifier (K) containing the copolymer (X). And from the viewpoint of improving the wettability of the molded product, preferably 20 to 85%, more preferably 30 to 80%; (B) is preferably 8 to 45 from the viewpoint of improving the wettability of the molded product and the productivity of (K). %, More preferably 10 to 40%; (C) is usually 70% or less, preferably from 5 to 65%, more preferably from 10 to 50% from the viewpoint of improving the mechanical strength and wettability of the molded article.

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 copolymer of (A) and (B) or (A), (B) and (C).
The form of the above [1] is (D), preferably in the presence of peroxide, (A) and (B) or (A), (B) and (C) are heated and melted, or in an appropriate organic solvent. It can be formed by suspending or dissolving, and further adding the chain transfer agent (t) and the polymerization inhibitor (f) as necessary and stirring with heating.
The form of the above [2] is (D), preferably in the presence of an azo compound, (A) and (B), or (A), (B) and (C) are heated and melted or suspended in a suitable organic solvent. It can be formed by turbidity or dissolution and, if necessary, adding a chain transfer agent (t) and a polymerization inhibitor (f) described later and stirring with heating.
Of the forms [1] and [2], the form [1] is preferable from the viewpoint of imparting wettability to a molded product to be described later.

[Resin modifier (K)]
The resin modifier (K) of the present invention comprises the polyolefin (A), unsaturated (poly) carboxylic acid (anhydride) (B) and ethylenically unsaturated monomer (C) as structural units, preferably 50 to It contains a modified polyolefin (X) having an acid value of 250 mgKOH / g.
The resin modifier (K) is used as a resin modifier for the polyolefin resin (E) described later.

[Polyolefin resin composition]
The polyolefin resin composition of the present invention comprises the resin modifier (K) and the polyolefin resin (E).
(E) includes a polymerization method exemplified as the production method of the above (A), or a degradation (thermal, chemical and mechanical degradation) method of a high molecular weight polyolefin (preferably Mn 80,000 to 400,000). For example, an ethylene unit-containing (propylene unit-free) (co) polymer, a propylene unit-containing (ethylene-unit-free) (co) polymer, an ethylene / propylene copolymer, and (Co) polymers of C4 or higher olefins are included.

  As a combination of (E) and (K), the case where the structural unit of (E) and the structural unit of the polyolefin (A) constituting (K) are the same or similar is the case of (E) and (K) It is preferable from the viewpoint of compatibility. For example, when (E) 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.

  Mn of (E) is preferably 10,000 to 500,000, more preferably 20,000 from the viewpoint of the mechanical strength of the molded article of the present invention described later and the compatibility with the resin modifier (K). ~ 400,000.

  The polyolefin resin composition of the present invention further includes a colorant (F1), a reinforcing agent (F2), a matting agent (F3), an antistatic agent (F4), and a dispersing agent 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 polyolefin resin composition of the present invention is usually 30% or less based on the total weight of the polyolefin resin composition. 10%.
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.

As a production method of the polyolefin resin composition of the present invention,
(1) A method (collective method) in which (E), (K) and, if necessary, (F) are mixed together to obtain a polyolefin resin composition (collective method);
(2) A masterbatch polyolefin resin composition containing a high concentration of (K) is prepared by mixing a part of (E), the total amount of (K), and if necessary, a part or all of (F). Then, a method (masterbatch method) including the remaining (E) and, if necessary, the remaining (F) and mixing to obtain a polyolefin resin composition is included.
The method (2) is preferable from the viewpoint of the mixing efficiency of (K).

  The weight ratio of (K) and (E) in the polyolefin resin composition of the present invention is preferably 0.1 / 99.9 to 50/50 from the viewpoint of the reformability and mechanical strength of the molded product described later, More preferably, it is 10 / 90-40 / 60, Especially preferably, it is 15 / 85-35 / 65, Most preferably, it is 20 / 80-30 / 70.

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 Co., Ltd.], etc., melting A method of kneading usually at 120 to 220 ° C. for 2 to 30 minutes using a kneading apparatus [batch kneader, continuous kneader (single screw kneader, biaxial kneader, etc.), 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.

[Molded articles and molded articles]
The molded product of the present invention is formed by molding the polyolefin resin composition.
Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), etc., depending on the purpose. Molding, multilayer molding, foam molding and the like can be performed by any method that incorporates means. Examples of the form of the molded product include a plate shape, a sheet shape, a film, and a fiber (including a nonwoven fabric).
Since the molded article of the present invention contains the resin modifier (K) having the carboxyl group or the like, it is excellent in affinity with paints, inks and the like having relatively high polarity.

The molded article 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 article.
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, acrylic urethane resin paint, and these so-called relatively high-polarity paints, Further, paints with low polarity (such as olefins) can also be used.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

Further, as a method for further 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, Examples include printing, screen printing, pad printing, dry offset printing, and offset printing.
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”. In addition, Examples 9, 15, 27 and 35 below are reference examples.

[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 2-7
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-7). The results are shown in Table 1.

(Remarks) Used raw material A0-1: Propylene 98 mol% and ethylene 2 mol% as structural units
Polyolefin [trade name "Sun Allomer PZA-20A", Sun
Allomer Co., Ltd., Mn 100,000]
A0-2: Propylene 80 mol%, 1-butene 20 mol% as a structural unit
Polyolefin [trade name “Toughmer XM-5080”, manufactured by Mitsui Chemicals, Inc., Mn 90,000]
A0-3: polyolefin having 100 mol% of propylene as a structural unit [trade name “L-MODU S600”, manufactured by Idemitsu Kosan Co., Ltd.,
Mn 35,000]

[Resin modifier]
Example 1
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 are distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain a resin modifier (K-1) containing the modified polyolefin (X-1). Obtained. (X-1) had an acid value of 95 and Mn of 5,000.

Examples 2-18, Comparative Examples 1-4
In Example 1, according to Tables 2 and 3, except that each used raw material was used, the same procedure as in Example 1 was carried out, and resin modifiers (K-2) to (K-18), (RK-1) to (RK-4) was obtained. The results are shown in Tables 2 and 3.

[Resin composition, molded product]
Examples 19-38, Comparative Examples 5-13
(K-1) to (K-18), (RK-1) to (RK-4), the thermal degradation product (A-1), commercially available polypropylene (E-1) [trade name “Sun Aromar PL500A” , Manufactured by Sun Allomer Co., Ltd.], commercially available polyethylene (E-2) [trade name “Novatech HJ490”, manufactured by Nippon Polyethylene Co., Ltd., Mn300,000] and commercially available ethylene / propylene copolymer (E-3) [ The product name “San Allomer PB222A”, manufactured by Sun Allomer Co., Ltd., Mn 350,000] was blended for 3 minutes in a Henschel mixer according to the blending composition (parts) in Table 4, and then 180 ° C. in a twin screw extruder with a vent. The polyolefin resin composition was obtained by melt-kneading under the conditions of 100 rpm and residence time of 5 minutes.
Each resin composition was molded at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. using an injection molding machine [trade name “PS40E5ASE”, Nissei Plastic Industry Co., Ltd.], and a predetermined test piece was prepared. Evaluation was made according to the method. The results are shown in Table 4.

<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: mN / m)
Wetting tension was measured according to JIS K6768. It shows that wettability is so favorable that wetting tension is large.

  From the results in Table 4, the polyolefin resin composition containing the modifier (K) containing (X) the modified polyolefin obtained by the method for producing the modified polyolefin of the present invention has excellent moldability, It can be seen that a molded product obtained by molding the composition is superior in mechanical strength and wettability compared to the comparative product.

  The modifier (K) containing the modified polyolefin obtained by the method for producing a modified polyolefin of the present invention is excellent in imparting wettability to water without lowering the mechanical strength of the molded article. Molded products formed from polyolefin resin compositions containing the quality agent (K) have an excellent balance between wettability and mechanical strength, so they are used in electrical and electronic equipment, packaging materials, transport materials, and daily life. It can be suitably applied to a wide range of fields such as materials and building materials.

Claims (11)

In the process for producing a modified polyolefin in which a polyolefin (A), an unsaturated (poly) carboxylic acid (anhydride) (B) and an ethylenically unsaturated monomer (C) are reacted in the presence of a radical initiator (D), Satisfying formulas (1) and (2), (A) has 0.1 to 20 double bonds per 1,000 carbon atoms, and (C) is a straight chain having 6 to 36 carbon atoms or A method for producing a modified polyolefin (X), which is a branched α-olefin.

0 <r _b × r _c <1.0 (1)

0 <r _c <1.5 (2)

[In the formulas (1) and (2), r _b is the reactivity ratio of (B) defined by r _b = k _bb / k _bc , and r _c is defined by r _c = k _cc / k _cb ( C) reactivity ratio; k _mn (m and n are each b or c) is a growth reaction rate constant, m is a monomer species at the growth end active site, and n is a monomer species to be added to the active site. Represent each. That is, k _bc when m is b and n is c represents a growth reaction rate constant when the monomer (C) is added to the monomer (B) at the active site, and m and n are k _{mn of} other combinations. Represents a growth reaction rate constant defined similarly. ]   The manufacturing method of Claim 1 in which (X) has an acid value of 50-250 mgKOH / g.   The production method according to claim 1 or 2, 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 manufacturing method according to any one of claims 1 to 3, wherein (A) is a thermal degradation product of a polyolefin 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 manufacturing method in any one of Claims 1-4.   Content based on the total weight of (A), (B) and (C) is (A) 20-85%, (B) 8-45%, (C) 5-65%. The manufacturing method in any one of 1-5.   The manufacturing method of the resin modifier (K) formed by containing the modified polyolefin (X) obtained by the manufacturing method in any one of Claims 1-6.   The manufacturing method of the polyolefin resin composition formed by containing the modifier (K) obtained by the manufacturing method of Claim 7, and polyolefin resin (E).   The method for producing a composition according to claim 8, wherein the weight ratio of (K) to (E) is from 10/90 to 40/60.   The manufacturing method of the molded article formed by shape | molding the composition obtained by the manufacturing method of Claim 8 or 9.   The manufacturing method of the molded article formed by giving and / or printing to the molded article obtained by the manufacturing method of Claim 10.