JP2008255207A - Surface-modified olefin resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method capable of using general olefin resin as a base material and obtaining an olefin resin excellent in dyeing property, adhesiveness, hydrophilic property and coating property by mild and simple processes not exerting a harmful influence on characteristics of the base material. <P>SOLUTION: An olefin resin is subjected to activation treatment and the olefin resin of which surface is activated by activation treatment is brought into contact with a polyamine compound and/or a polyimine compound to produce the surface-modified olefin resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a surface-modified polyolefin resin having good dyeability, adhesiveness, hydrophilicity, and paintability and a method for producing the same, and more specifically, a high-molecular polyamine compound and / or polyimine compound includes The present invention relates to a surface-modified polyolefin resin having good dyeability, adhesiveness, hydrophilicity, and paintability, which is bonded to a polyolefin main chain via an amide group or amino group, or its imino group, and a method for producing the same.

Olefin resins have advantages such as ease of processing and high chemical resistance, so they are processed into fibers, sheets, molded products, etc., and used for various applications. On the other hand, olefin resins have the disadvantages that they are low in polarity and high in crystallinity, so that they have low affinity with other materials and are difficult to bond and dye. For this reason, the utilization is not progressing in some fields of the textile field.
Polypropylene, in particular, had many advantages such as lightness, strength, and high chemical resistance at the beginning of development. It is not used much.

  Conventionally, as a method of coloring polypropylene, a method of adding a pigment to melted polypropylene and then forming a fiber (referred to as “original”) is known.

The coloring by the original attachment has a problem that it is difficult to obtain a clear color, and the polypropylene resin becomes hard and flexibility is easily lost. Moreover, since it is necessary to color in advance, there is a problem that flexibility is low and it is difficult to cope with small-scale production or temporary production.
For this reason, the present condition is that the fiber manufactured by this method is used only for limited uses, such as a carpet.

  On the other hand, there has been proposed a technique for improving dyeability by modifying an olefin resin, particularly polypropylene resin itself.

For example, in Japanese Patent Application Laid-Open No. 2003-138421 (Patent Document 1), polymerized by a metallocene catalyst, (1) MFR is 5 to 100 g / 10 min characteristic, (2) Q value is 1.5 to 4.0 characteristic. (3) Tm is 110 to 140 ° C., (4) T ₈₀ -T ₂₀ is 10 ° C. or less, (5) 0 ° C. soluble content at TREF measurement is 3 wt% or less, (6) α-olefin content Is obtained by blending a polymer type antistatic agent with a propylene / α-olefin random copolymer having a characteristic of 1 to 18 mol% of (7) C _{12 to} C ₃₀ oligomer component amount of 60 wtppm or less An excellent polypropylene fiber is disclosed.

  However, although this polypropylene fiber has good dyeability, it is mainly composed of a special propylene / α-olefin random copolymer and cannot be applied to a general polyolefin resin.

  On the other hand, in JP-A-7-90783 (Patent Document 2), the surface of a polyolefin resin is activated by ozone treatment, and then the activated polyolefin resin is grafted with acrylamide, methacrylamide, etc. while irradiating with ultraviolet rays. A polyolefin resin surface modification method and a dyeing method are disclosed in which a polyolefin resin is surface-modified by copolymerization, and a grafted amide group is Hoffmann-transferred to further improve dyeability.

  However, this method is a method in which a polyolefin resin is surface-treated by graft copolymerization in which the vinyl group of acrylamide is cut and undergoes an addition reaction, and in order to proceed with the graft copolymerization, in addition to ozone treatment, it is relatively long. The ultraviolet irradiation of time is essential. For this reason, there is still a possibility that the strength of the surface-modified polyolefin resin may be reduced due to the cutting of the polyolefin main chain or the like.

  In this method, since a vinyl compound having about 3 to 20 carbon atoms having an amide group is used, it is necessary to enhance the graft ratio and / or the side chain lengthening in order to improve the dyeability. There are problems associated with achieving it, or that it is difficult to achieve in the first place.

  That is, in this method, it is necessary to increase the concentration of acrylamide and the like in order to increase the graft rate (the graft rate decreases when the concentration is low), but the presence of this high concentration of acrylamide and the like is the reaction step. A large amount of the by-product of the homopolymer is produced therein, which causes a decrease in polymerization efficiency. In addition, since the presence of this homopolymer causes clogging in substrates such as woven fabrics and non-woven fabrics, in this method, after the surface modification treatment, strict washing (for example, washing with 100 ml of toluene for 2 hours, 3 hours) And the clogging needs to be removed.

Further, as is apparent from the process, this method requires three steps of ozone treatment, ultraviolet irradiation, and Hoffman rearrangement, and requires a relatively long time for grafting the monomer. There has been a demand for a simpler and quicker method suitable for the above.
JP 2003-138421 A JP-A-7-90783

  An object of the present invention is to obtain an olefin resin having good dyeability by a gentle and simple process which can use a general olefin resin as a base material and does not adversely affect the properties of the base material. An object of the present invention is to provide a method for producing a surface-modified olefin resin. Another object of the present invention is that a general olefin resin can be used as a base material, and the adhesiveness, hydrophilicity, and the like by a gentle and simple process that does not adversely affect the characteristics of the base material. An object of the present invention is to provide a method for producing a surface-modified olefin resin capable of obtaining an olefin resin excellent in paintability.

  Another object of the present invention is that a polymer, that is, a polyamine compound and / or polyimine compound containing a large amount of nitrogen atoms is bonded to the polyolefin main chain via its amide group or amino group or its imino group. It is to provide a surface-modified polyolefin resin having good dyeability, adhesion, hydrophilicity, and paintability.

  As a result of intensive studies to solve the above problems, the present inventor has activated the olefin resin, and the activated olefin resin contains a polyamine compound containing a large number of amide groups or amino groups and / or When a polyimine compound containing a large number of imino groups is brought into contact, surface modification with the polyamine compound proceeds under mild conditions without requiring special reaction promoting means such as ultraviolet irradiation, and the resulting surface modification The olefin resin was found to be very excellent in dyeability, adhesiveness, hydrophilicity, and paintability, and the present invention was completed.

  That is, the main aspect of the present invention is that, in one main aspect, the olefin resin is activated, and the olefin resin whose surface is activated by this activation treatment is converted into a polyamine compound and / or a polyimine compound, preferably 1,000. The present invention provides a method for producing a surface-modified olefin resin, characterized by contacting with a polyamine compound and / or a polyimine compound having a molecular weight of ˜200,000.

  In another main aspect of the present invention, the polyamine compound and / or the polyimine compound, preferably a polyamine compound and / or a polyimine compound having a molecular weight of 1,000 to 200,000, is an amino group in at least a part of the polyolefin. Alternatively, the present invention provides a surface-modified olefin resin, which is bonded through an amide group or an imino group.

  Here, the weight average molecular weight (Mw) of the polymer in this specification means a value measured by a gel permeation chromatography (GPC) method using a Hitachi L-6000 type high performance liquid chromatograph. Hitachi L-6000 is used as an eluent flow path pump, a Shodex RI SE-61 differential refractive index detector is used as a detector, and an GS-220HQ (exclusion limit molecular weight: 3,000) of an aqueous gel filtration type of Asahi Pack is used as a column. ) And GS-620HQ (exclusion limit molecular weight 2 million) were used in a double connection. The sample was adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl was used. As an eluent, a 0.4 mol / liter sodium chloride aqueous solution was used. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve was determined using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard sample, and the Mw of the polymer was determined based on the calibration curve.

Next, the basic scheme of the production method of the present invention will be outlined.
In the production method of the present invention, as described above, the olefin resin is first activated. This “activation treatment” introduces functional groups or unsaturated bonds containing oxygen, nitrogen, etc. on the surface of the resin by performing ozone treatment, flame treatment, various discharge treatments, etc. on the olefin resin. It is processing to do. When the activation treatment is performed by flame (flame) treatment or various discharge treatments, radicals are generated in the olefin resin, which reacts with oxygen, water vapor, etc., and on the surface of the olefin resin, percarbonate groups, carbonyl groups, carboxyls. Groups, hydroxyl groups and the like are formed. Further, when the activation treatment is performed by ozone treatment, a percarbonate group is introduced into the olefin resin, which changes to a carbonyl group, a carboxyl group, a hydroxyl group, or the like.

  In the production method of the present invention, before these functional groups are further reacted with oxygen, hydrogen, and water vapor and stabilized, a polyamine compound having a large number of amino groups or amide groups and / or a large number of imino groups are added to the olefin resin. The polyimine compound having the above-mentioned reaction, the percarbonate group, the carbonyl group, or the carboxyl group is reacted with an amino group, an amide group, and / or an imino group (mainly dehydration condensation reaction), and the olefin resin has an amino group, A polyamine compound and / or a polyimine compound is bonded via an amide group and / or an imino group.

As a method of contacting with a polyamine compound and / or a polyimine compound, a method of immersing an olefin resin in a polyamine compound and / or a solution of the polyimine compound (room temperature to 80 ° C.) for several seconds to 10 minutes, and then washing with water, similarly, There is a method of dipping in a solution of a polyimine compound and heat drying.
Further, the olefin resin is placed in the atmosphere until it is immersed in the solution of the polyamine compound and / or polyimine compound after the activation treatment, preferably a rare gas (argon, neon, helium) or nitrogen, or a mixed gas thereof. It is better to put it in the atmosphere.

  In the present invention, the point to be particularly noted is that, unlike the graft copolymerization reaction of a vinyl monomer having an amino group, a polyamine compound is bonded to the olefin resin via an amino group or an amide group, or via an imino group. This is the point that the polyimine compound is bound. For this reason, surface modification | reformation is enabled, without requiring the excessive conditions which can degrade the characteristics of olefin resin, such as ultraviolet irradiation.

  In the present invention, the polyamine compound containing a large number of amino groups or amide groups and / or the polyimine compound containing a large number of imino groups are brought into contact with the olefin resin, thereby causing the functional group generated by the activation treatment to occur. It should also be noted that there are many opportunities for response.

  Further, in the present invention, an amino group, an amide group, and a polyamine compound that contain a large number of amino groups or amide groups and / or a polyimine compound that contains a large number of imino groups are bonded to an olefin resin. It should be noted that the imino group is efficiently introduced. In the present invention, by introducing a large number of amino groups, amide groups and / or imino groups with polyamine compounds and / or polyimine compounds in this way, high dyeability and adhesiveness as demonstrated in the examples described later are achieved. is doing. Further, the bond formed between the percarbonate group, carbonyl group or carboxyl group and the amino group, amide group or imino group is relatively strong, and is high as demonstrated in the examples described later. It enables dyeing with fastness. Furthermore, it is excellent in adhesiveness, hydrophilicity, and paintability.

1. Production method of modified polyolefin resin of the present invention (1) Activation treatment In the production method of the present invention, as described above, the olefin resin is first activated.

  In this specification, there is no restriction | limiting in particular about the olefin resin to activate, and a general olefin resin can be used. Specific examples include, for example, homopolymers of any α-olefin such as ethylene, propylene, butene-1, pentene-2, hexene-1, 4-methyl-pentene-1, octene-1, or the like. There are, but are not limited to, copolymers of more than one species, or homopolymers and / or copolymers of these. A suitable example of the present invention is a homopolymer of polypropylene or polyethylene, or a copolymer or random copolymer of propylene or ethylene with another α-olefin, which can be said to be a typical typical resin that is difficult to dye. .

  The olefin resin subjected to the surface modification treatment is usually a molded product, for example, a long fiber shape, a short fiber shape, a yarn shape, a thread shape, a fabric shape, a knitted shape, a non-woven fabric shape, a film shape, a sheet shape, a tubular shape. , Rod-shaped, hollow container-shaped, box-shaped, foamed body, laminated body and the like, but are not limited thereto.

  In the present invention, an olefin resin to which additives such as a stabilizer, a nucleating agent, a flame retardant, a filler, and a foaming agent are added may be used as long as the modification described below is not significantly impaired.

  The activation treatment of the olefin resin in the present invention may be any treatment that can introduce a functional group containing oxygen, nitrogen or the like or an unsaturated bond into the olefin resin. For example, plasma treatment, corona discharge treatment, flame (flame) treatment. It can be performed using various known methods such as ozone treatment.

  When performing the plasma treatment, for example, an olefin resin is subjected to glow discharge in an atmosphere of a rare gas (argon, neon, helium), nitrogen gas, nitrogen, carbon dioxide gas, oxygen, or a mixed gas containing two or more of these. Exposure to the generated plasma may generate radicals on the surface of the olefin resin. The plasma generation conditions in the present invention are preferably a frequency of 13.56 MHz, an irradiation output of 10 to 2000 W, and an irradiation time of 0.01 seconds to 10 minutes. As the atmosphere gas, air, or rare gases (argon, neon, helium), nitrogen, oxygen, and carbon dioxide can be used singly or in combination. Preferably, a mixed gas of at least one kind of rare gas (argon, neon, helium) and nitrogen and oxygen or carbon dioxide gas is used.

When performing the corona discharge treatment, in the atmosphere or in an atmosphere using a rare gas (argon, neon, helium), nitrogen, oxygen, or carbon dioxide alone, or at least a rare gas (argon, neon, helium) and nitrogen. A corona discharge is generated by applying a high voltage of thousands to tens of thousands of volts between the electrodes in an atmosphere of a mixed gas of one kind and oxygen or carbon dioxide gas, and the olefin resin passes between the electrodes during the discharge. By doing so, the surface of the olefin resin can be activated. In the corona discharge used in the present invention, it is preferable to the discharge amount and 0.1～5000W · min / ^{m 2,} and more preferably a 10～1500W · min / ^{m 2.}

(2) Contact with polyamine compound and / or polyimine compound In the production method of the present invention, the olefin resin whose surface is activated by the activation treatment is then contacted with the polyamine compound and / or polyimine compound.

  In the present invention, “the surface is activated” means that the olefin resin has, on at least a part of its surface, oxygen or the like capable of reacting with an amide group or amino group of a polyamine compound or an imino group of a polyimine compound. It means a state in which a functional group (for example, a percarbonate group, a carbonyl group, a carboxyl group) or an unsaturated bond is held, and in the present invention, these functional groups are oxygen, hydrogen, water vapor, and the like. Prior to further reaction and stabilization, the olefin resin must be contacted with a polyamine compound and / or a polyimine compound.

  The timing of bringing the activated olefin resin into contact with the polyamine compound varies depending on various treatment means, its conditions, and the olefin resin, polyamine compound, polyimine compound and the like to be used, but the activation treatment is performed after the activation treatment. When the surface tension of the olefin resin is 1.1 times or more the surface tension of the olefin resin before the active treatment, the activated olefin resin is preferably brought into contact with the polyamine compound and / or polyimine compound, It is more preferable that the contact is made at the time of 1.3 times or more, and the contact is particularly preferably made at the time of 1.5 times or more.

  Further, if the surface tension ratio is 1.5 times or more, it may be directly contacted with a polyamine compound and a polyimine compound (usually a solution), but when the surface tension ratio is 1.1 times or more and less than 1.5 times Since the activated olefin resin and the polyamine solution may be difficult to adjust, after contact with a solution having a low surface force (for example, a mixture of water and alcohol), the polyamine compound and / or polyimine compound ( It is preferable to contact with a normal solution).

Here, “surface tension” means a value of surface tension measured according to the following measurement procedure. The measurement is performed in a standard test room atmosphere (JIS K 7100) at a temperature of 23 ° C. and a relative humidity of 50%.
A sample such as a woven fabric, a knitted fabric, or a non-woven fabric whose surface tension is to be measured is cut into a 10 cm square immediately before the measurement, and used as a test piece. The test liquid mixture is ethylene glycol monoethyl ether (ethyl cellosolve), formamide (special grade of JIS K 8873 or higher), methanol (JIS K 6768) according to JIS K 6768 “Table liquid mixture for wetness measurement of plastic films and sheets”. K 8891) and water prepared by stepwise mixing are used.
The determination of the surface tension is performed by dropping several drops of the test liquid mixture onto the test piece with a dropper and evaluating the state of the liquid drop after 30 seconds. If the droplet soaks in the test piece in less than 30 seconds, the process proceeds to the test mixture with the next highest surface tension. Conversely, if it takes 30 seconds or more, the next lower surface tension is obtained. Proceed to test mixture. This operation is repeated, and a mixed solution to be immersed in the test piece in 30 seconds is selected. This operation is performed at least three times, and the surface tension of the liquid mixture thus selected is defined as the surface tension of the substrate.
When the sample is in the form of a film or a sheet, it is performed in accordance with JIS K 6768 “Plastic-film and sheet-wetting tension test method”.

[式中のＲ_１、Ｒ_２、Ｒ_３は、それぞれ同一であっても異なっていてもよく、非反応性の原子又は有機基を表し、Ｒ_１とＲ_２は互いに結合して環を形成していても良く、ｎは、２０〜２０００の整数を表す。]
式中のＲ_１、Ｒ_２、Ｒ_３としては、水素原子、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、複素環基及びアルコキシ基等を例示できる。この場合、アルキル基としては、メチル、エチル、プロピル、ブチル、ベンチル、イソピロピル、イソブチル等を含む炭素数１〜１０のアルキル基が好ましく、炭素数１〜８のアルキル基がより好ましく、炭素数１〜５アルキル基がさらに好ましく、炭素数１〜３のアルキル基が特に好ましい。
また、アルケニル基としては、ビニル、アリル等を含む、炭素数２〜１０のアルケニル基が好ましく、炭素数２〜８のアルケニル基がより好ましく、炭素数２〜５のアルケニル基がさらに好ましく、炭素数２〜４のアルケニル基が特に好ましい。
また、アルキニル基としては、エチニル基、１-プロピニル基、１−ヘプチニル基などの、炭素数２〜１８のアルキニル基が好ましく、炭素数２〜１０のアルキニル基がより好ましく、炭素数２〜６のアルキニル基がさらに好ましく、炭素数２〜４のアルキニル基が特に好ましい。
また、シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基などの、炭素数３〜１０のシクロアルキル基が好ましく、炭素数３〜６のシクロアルキル基がより好ましく、炭素数５〜６のシクロアルキル基が特に好ましい。
また、アリール基としては、フェニル、トリル、ナフチル等の炭素数６〜１０のアリールが好ましい。
また、複素環基としては、例えば、フラン環、オキサゾール環、イソオキサゾール環、テトラヒドロフラン環などの５員環、ピラン環などの６員環、ベンゾフラン環、イソベンゾフラン環、ジベンゾフラン環、キサントン環、キサンテン環、クロマン環、イソクロマン環、クロメン環などの縮合環に代表されるヘテロ原子として酸素原子を含む複素環、あるいは、例えば、チオフェン環、チアゾール環、イソチアゾール環、チアジアゾール環、ベンゾチオフェン環などに代表されるヘテロ原子として硫黄原子を含む複素環、さらに、例えば、ピロール環、ピラゾール環、イミダゾール環、トリアゾール環、ピロリジン環などの５員環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、モルホリン環などの６員環、インドール環、インドレン環、イソインドール環、インダゾール環、インドリン環、イソインドリン環、キノリン環、イソキノリン環、キノリンキノリン環、キノキサリン環、キナゾリン環、フタラジン環、プリン環、カルバゾール環、アクリジン環、ナフトキノリン環、フェナントロジン環、フェナントロリン環、ナフチリジン環、ベンゾキノリン環、フェノキサジン環、フタロシアニン環、アントラシアニン環などの縮合環に代表されるヘテロ原子として窒素原子を含む複素環などが挙げられる。
また、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基などの炭素数１〜１０、好ましくは１〜６のアルコキシ基が挙げられる。 The “polyamine compound” used in the present invention includes a primary amine (R—NH ₂ , a secondary amine (R ₂ —NH), a tertiary amine (R ₃ —N), or a derivative thereof ( For example, a polymer or copolymer having an amide (R—CONH ₂ ), wherein R is a hydrocarbon group, preferably a carbon group selected from the group consisting of alkyl, aryl, aralkyl, alkenyl and alkynyl. A hydrogen group, more preferably an alkyl having 1 to 10 carbon atoms, preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, such as methyl, ethyl, propyl, butyl, ventil, isopropyl, and isobutyl; vinyl , Alkenyl having 2 to 10 carbon atoms, preferably 2 to 8, more preferably 2 to 5, particularly preferably 2 to 4 carbon atoms such as allyl; and phenyl, tolyl, naphthyl and the like It refers to a hydrocarbon radical selected from the group consisting of aryl prime 6-10).
The “polyimine compound” used in the present invention is a compound represented by the following formula:

[In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each represents a non-reactive atom or organic group, and R ₁ and R ₂ are bonded to each other to form a ring. N may represent an integer of 20 to 2000. ]
Examples of R ₁ , R ₂ and R ₃ in the formula include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group and an alkoxy group. In this case, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms including methyl, ethyl, propyl, butyl, benzyl, isopropyl, isobutyl, etc., more preferably an alkyl group having 1 to 8 carbon atoms, and 1 carbon atom. To 5 alkyl groups are more preferable, and alkyl groups having 1 to 3 carbon atoms are particularly preferable.
Moreover, as an alkenyl group, a C2-C10 alkenyl group containing vinyl, an allyl, etc. is preferable, A C2-C8 alkenyl group is more preferable, A C2-C5 alkenyl group is more preferable, Carbon The alkenyl group having 2 to 4 is particularly preferable.
Moreover, as an alkynyl group, C2-C18 alkynyl groups, such as an ethynyl group, 1-propynyl group, and 1-heptynyl group, are preferable, C2-C10 alkynyl groups are more preferable, and C2-C6 Are more preferable, and an alkynyl group having 2 to 4 carbon atoms is particularly preferable.
Moreover, as a cycloalkyl group, C3-C10 cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, are preferable, and a C3-C6 cycloalkyl group is more. A C5-C6 cycloalkyl group is particularly preferable.
Moreover, as an aryl group, C6-C10 aryl, such as phenyl, tolyl, and naphthyl, is preferable.
Examples of the heterocyclic group include a 5-membered ring such as a furan ring, an oxazole ring, an isoxazole ring, and a tetrahydrofuran ring, a 6-membered ring such as a pyran ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a xanthone ring, and a xanthene. A heterocycle containing an oxygen atom as a heteroatom represented by a condensed ring such as a ring, chroman ring, isochroman ring, chromene ring, or a thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiophene ring, etc. Heterocycles containing a sulfur atom as a representative heteroatom, for example, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, 5-membered ring such as pyrrolidine ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine Ring, 6-membered ring such as morpholine ring, Ring, indolen ring, isoindole ring, indazole ring, indoline ring, isoindoline ring, quinoline ring, isoquinoline ring, quinoline quinoline ring, quinoxaline ring, quinazoline ring, phthalazine ring, purine ring, carbazole ring, acridine ring, naphthoquinoline Examples thereof include heterocycles containing a nitrogen atom as a hetero atom typified by a condensed ring such as a ring, a phenanthrozine ring, a phenanthroline ring, a naphthyridine ring, a benzoquinoline ring, a phenoxazine ring, a phthalocyanine ring, and an anthocyanin ring.
Moreover, as an alkoxy group, C1-C10, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, Preferably the alkoxy group of 1-6 is mentioned.

  Specific examples of suitable polyamine compounds and polyimine compounds used in the present invention include polyethyleneimine, polyvinylamine, polyallylamine, and aromatic amine.

  In the present invention, polyamine compounds and polyimine compounds having a molecular weight of 1,000 or more can be preferably used. However, the reactivity with the olefin after the activation treatment and the dyeability of the finally obtained modified olefin are improved. In order to further increase, a higher polymer is more preferable. Specifically, those having a molecular weight of 1,000 to 200,000 are preferred, those having a molecular weight of 3,000 to 200,000 are more preferred, and those having a molecular weight of 15,000 to 200,000 are particularly preferred.

  In the present invention, there is no particular limitation on the form in which the polyamine compound and / or polyimine compound is brought into contact with the olefin resin, but for ease of handling, the polyamine compound and / or polyimine compound is dissolved in various solvents, It is preferable to contact the two by immersing the olefin resin in the solution.

  In addition, the solvent used in this case is not particularly limited as long as it can be dissolved. For example, water, methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, secondary butyl alcohol, and tertiary. Alcohol solvents such as butyl alcohol; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, and methyl benzoate Aliphatic hydrocarbon solvents such as normal hexane, normal heptane and normal octane; alicyclic hydrocarbon solvents such as cyclohexane and ethylcyclohexane; There are ketone solvents such as seton, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and petroleum solvents, etc., but the solubility of polyamine compounds and polyimine compounds is good and handling The simplest water is preferred.

Moreover, what is necessary is just to select immersion time, temperature, etc. suitably according to the olefin resin to be used, a polyamine compound, a polyimine compound, and a solvent, but typically it immerses for several seconds-about 10 minutes at about normal temperature-about 80 degreeC.
Further, the olefin resin is placed in the atmosphere until it is immersed in the solution of the polyamine compound and / or polyimine compound after the activation treatment, preferably a rare gas (argon, neon, helium) or nitrogen, or a mixed gas thereof. It is better to put it in the atmosphere.

  After the treatment with the polyamine compound and / or polyimine compound, it is usually preferable to remove the reaction solution and the like. Although not necessarily required, for example, it is preferable to remove the unreacted polyamine compound by washing the treated olefin resin with hot water or the like. However, in one embodiment, it can be subjected to heat drying as it is.

However, in the reaction process of the present invention, it is not necessary to use a high concentration reaction solution, and there is no generation of by-products (homopolymer) by the graft polymerization method. Even so, there is almost no clogging in the surface-modified woven fabric, knitted fabric or non-woven fabric, or it can be easily removed.
Moreover, if the polyamine compound and / or polyimine compound which remained unreacted in the reaction step is washed with warm water of 20 to 80 ° C. for about 1 to 10 minutes, for example, a woven fabric made of olefin resin, knitted fabric or Even when the surface of a nonwoven fabric or the like is modified, it can be almost completely removed from the surface-modified woven fabric, knitted fabric or nonwoven fabric.

  Furthermore, unlike the graft polymerization method, a polyamine solution or a polyimine solution used as a reaction solution can be reused because it does not produce a homopolymer, and is very efficient and suitable for industrialization.

2. Surface-modified olefin The surface-modified olefin resin obtained by the production method of the present invention comprises a polyamine compound and / or a polyimine compound, preferably a polyamine compound having a molecular weight of 1,000 to 200,000, and / or at least a part of the polyolefin. Alternatively, the surface of the olefin resin is modified by bonding a polyimine compound via its amino group or amide group or its imino group, respectively.

  The surface-modified olefin resin of the present invention has a large amount of amide group or amino group introduced by constituting a side chain with a high molecular polyamine compound, thereby enabling high dyeability, adhesiveness, hydrophilicity, and The paintability can be achieved. In addition, the surface-modified olefin resin of the present invention can achieve high dyeing fastness because it has excellent reactivity particularly with respect to anionic dyes and binds firmly to the dyes.

  Moreover, regarding adhesiveness, the outstanding adhesive force with respect to a cyanoacrylate type | system | group and an epoxy-type adhesive agent can be provided.

  Further, as described above, the surface-modified olefin resin of the present invention is produced under very mild conditions, so that the main chain of the polyolefin is hardly cut and the original characteristics are hardly deteriorated. It is.

  Specifically, the surface-modified olefin resin of the present invention preferably has a number average molecular weight of 10,000 to 500,000, more preferably a number average molecular weight of 30,000 to 200,000. In addition, properties resulting from polyolefins such as chemical resistance, mechanical strength, heat resistance, recycling, stiffness and softness are almost retained even after surface modification.

  On the other hand, in the surface-modified olefin resin of the present invention, the ratio of the polyamine compound and the polyimine compound in the whole resin is usually 0.001 to 5% by weight. However, the polyamine compound and the polyimine compound are usually polymers having a molecular weight of 1,000 or more as described above, and very many amide groups or amino groups are present in the surface-modified olefin resin.

  The polyolefin constituting the surface-modified olefin resin of the present invention is the same as that described for the olefin resin, and typical examples thereof include polyethylene or polypropylene, or ethylene or propylene and other α-olefins. Or a random copolymer.

  The surface-modified olefin resin of the present invention takes advantage of the properties imparted by surface modification with a polyamine compound, and is an antistatic material, a gas adsorbing material, various metal chelating materials, a paint / dye waste liquid collecting material, an ink jet printing cloth; a bumper It can be used for various industrial materials such as automobile parts such as instrument panels and trims; and building materials used for interiors such as decorative sheets and baseboards.

  Examples of the dye applicable to the surface-modified olefin resin of the present invention include a direct dye, an acid dye, a reactive dye, a vat dye, a vegetable dye, a sulfur dye, and a naphthol dye.

  The acid dye is a dye mainly used for dyeing protein fibers such as silk and wool and nylon fibers, and is a dye that ionically bonds to fibers through an anionic group such as a sodium sulfonate group. Examples of the dye include azo series, anthraquinone series, triphenylmethane series, and xanthene series.

  The reactive dye is soluble in water and anionic in water. Reacts with the hydroxyl group of cellulose fiber to form a covalent bond. The reactive group of the dye includes a vinyl sulfone type and a monochlorotriazine type, and these are strongly bonded to a hydroxyl group of cellulose through a nucleophilic addition reaction or a nucleophilic substitution reaction, and excellent fastness is obtained. Reactive dyes have a pigment matrix similar to acid dyes, such as pyrazolone azo (yellow), γ acid azo (orange), H acid azo (red), anthraquinone (blue), etc. is there.

  The direct dye has a relatively large molecular weight among water-soluble anionic dyes and has an affinity for cellulose fibers. Although the dyeing operation is easy and relatively inexpensive, there are drawbacks in that the hue is not clear and light resistance and washing fastness are generally low. Also, most of the dye molecules are sodium salts of chromic acid having an azo group and containing water-soluble sulfonic acid.

  Vat dyes are insoluble in water, but when they are reduced with a reducing agent under alkaline conditions, they become water-soluble leuco bodies that are dyed onto fibers and oxidized by air or the like. This dye includes an indigo type and an anthraquinone type.

  Plant dyes are dyes mainly composed of pigments extracted from roots, trunks, bark, leaves, flowers, fruits and the like of various plants. Many materials are useful, such as Akane, Kariyasu, Nigiri, Suo, Murasaki, Onion, Shabu, and Kuri. In dyeing, a metal compound having a valence of 2 or more (a salt of iron, copper, aluminum, chromium, or the like) may be used as a mordant.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to the following examples.

Example 1
A polypropylene woven fabric (manufactured by MRC Pyrene Co., Ltd., PP taffeta (75 denier)) was used as a base material. The surface tension of the polypropylene woven fabric before plasma treatment was confirmed to be 32 mN / m by dropping a wet tension test mixture (manufactured by Wako Pure Chemical Industries, Ltd.) according to the method described in [0036]. Plasma treatment is performed on both surfaces of this polypropylene woven fabric using a plasma processing machine (model number BP-1) manufactured by Samco International Laboratory, and a mixed gas of oxygen and argon (Ar) (oxygen concentration 50% by volume, every flow rate) Min. 40 ml) The conditions were as follows: atmosphere, degree of vacuum 0.1 Torr, frequency 13.56 MHz, output 50 W, irradiation time 30 seconds.

  Several minutes after the completion of the plasma treatment, the treated polypropylene woven fabric is taken out, and the surface tension of the polypropylene woven fabric activated by the plasma treatment is determined according to the method described in [0036]. It was 50 mN / m when confirmed by dripping Kogure Pharmaceutical Co., Ltd.). The taken-out polypropylene non-woven fabric was reacted for several minutes by dipping in a 0.1% by weight aqueous solution of polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight 70,000) prepared in advance at 20 ° C. .

After the reaction, the polypropylene woven fabric treated with polyethyleneimine was taken out, rinsed with running water (H ₂ O) at 60 ° C. for about 10 minutes (flow rate 5 liter / min), and unreacted polyethyleneimine was removed.

  Next, the dye was added to Remazol dye Brill. 210 g of Blue G (manufactured by Dystar), 210 mg of dye dispersant (multifine, manufactured by Senka Co., Ltd.), 8.4 g of mirabilite (manufactured by Wako Pure Chemical Industries, Ltd.), and soda ash (Wako Pure Chemical Industries, Ltd.) 4 .2 g and dissolved in 210 ml of water (temperature 50 ° C.), a portion of the woven fabric (7 g) was prepared with the adjusted dye, and the high-pressure test machine (LHD-308-2E, Sakurai dyeing industry ( ), And dyed in an atmosphere of 1 atmosphere at 50 ° C. for 90 minutes.

  After dyeing, the woven fabric was soaped with a soaping agent obtained by dissolving 2 g of Bisnor AD (one company, Yushi Kogyo Co., Ltd.) in 1 liter of water at 90 ° C. for 10 minutes.

(Comparative Example 1)
A polypropylene woven fabric was treated and dyed in the same manner as in Example 1 except that the plasma treatment was not performed to obtain a final product. However, the obtained product was not dyed at all.

(Evaluation)
For the dyed fabric obtained in Example 1, the fastness to washing test (JIS L 0844 A-1 method), the fastness test against light and sweat (JIS L 0888 B method), and the fastness to friction test (JIS L 0849 II). Shape) to evaluate the fastness of dyeing. The results are summarized in the following table.

(Example 2)
The polyethyleneimine is treated in the same manner as in Example 1 except that it is changed to an aqueous solution of 0.1% by weight of polyallylamine (manufactured by Nitto Boseki Co., Ltd., PAA-HCl-3L, weight average molecular weight 15,000) and used for dyeing. For woven fabric.

  Next, 300 mg of Indanthren dye Blue BC coll (manufactured by DYSTAR) as a dye, 100 mg of leveling agent (manufactured by Yushi Kogyo Co., Ltd., KYA-800B), 2 g of caustic soda 38 ° Be (manufactured by Wako Pure Chemical Industries, Ltd.), hydro It was dissolved in 0.6 g of sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 ml of water (60 ° C.) to obtain a dye.

With this prepared dye, 10 g of the woven fabric after the treatment was dyed with a high-pressure dyeing machine (Sakai Dyeing Machine Co., Ltd., LHD-308-2E) at 60 ° C. for 60 minutes. After dyeing, the woven fabric dyed in a solution (50 ° C.) in which 3 ml of hydrogen peroxide H ₂ O ₂ (35%) was dissolved in 1 l of water was immersed for 10 minutes to be oxidized.

  After dyeing, soaping was performed on the woven fabric with a soaping agent in which 2 g of leveling agent (manufactured by Yufu Kogyo Co., Ltd., KYA-800B) was dissolved in 1 liter of water at 90 ° C. for 10 minutes.

(Comparative Example 2)
Except that the plasma treatment was not performed, the polypropylene woven fabric was treated and dyed in the same manner as in Example 2 to obtain a final product. However, the obtained product was not dyed at all.

(Evaluation)
For the dyed fabric obtained in Example 2, the fastness to washing test (JIS L 0844 A-1 method), the fastness test against light and sweat (JIS L 0888 B method), and the fastness to friction test (JIS L 0849 II). Shape) to evaluate the fastness of dyeing. The results are summarized in the following table.

(Example 3)
A woven fabric for dyeing was obtained in the same manner as in Example 1 except that polyethyleneimine was changed to an aqueous solution containing 0.1% by weight of polyvinylamine (manufactured by Daianitrix Co., Ltd., molecular weight 60,000).

  Next, as a dye, 200 mg of Telon dye Blue AFN (manufactured by Dystar) was dissolved in 200 mg leveling agent (manufactured by Senka Co., Ltd., Migre Girl N-11E), 0.4 g of sodium sulfate, 4 g of acetic acid, and 200 ml of water to obtain a dye.

  With this prepared dye, 7 g of the treated woven fabric was dyed with a high-pressure dyeing machine (Sakai Dyeing Machine Co., Ltd., LHD-308-2E) at 100 ° C. for 90 minutes in an atmosphere of 1 atm.

  After dyeing, the woven fabric was soaped with a soaping agent obtained by dissolving 2 g of Bisnor AD (one company, Yushi Kogyo Co., Ltd.) in 1 liter of water at 90 ° C. for 10 minutes.

(Comparative Example 3)
Except that the plasma treatment was not performed, the polypropylene woven fabric was treated and dyed in the same manner as in Example 3 to obtain a final product. However, the obtained product was not dyed at all.

(Evaluation)
For the dyed fabric obtained in Example 3, the fastness to washing test (JIS L 0844 A-1 method), the fastness test against light and sweat (JIS L 0888 B method), and the fastness to friction test (JIS L 0849 II). Shape) to evaluate the fastness of dyeing. The results are summarized in the following table.

Example 4
A polypropylene film having a thickness of 0.5 mm was prepared, and after degreasing the surface with methanol, a test piece having a size of 25 mm × 100 mm was prepared.
Plasma treatment was performed on both sides of the produced polypropylene film using a plasma processing machine (model number BP-1) manufactured by Samco International Laboratories Co., Ltd., and a mixed gas of oxygen and argon (oxygen concentration 50 vol%, flow rate 40 ml / min) ) It was performed under the conditions of atmosphere, vacuum degree 0.1 Torr, frequency 13.56 MHz, output 30 W, irradiation time 30 seconds.

  After the plasma treatment was completed, the treated polypropylene film was immersed for several minutes in a 0.1% by weight aqueous solution of polyvinylamine (Daanitrix Co., Ltd., molecular weight 60,000) prepared at 20 ° C. in advance. And reacted.

  After the reaction, a polypropylene film treated with polyvinylamine was taken out, rinsed with running water at 60 ° C. for about 5 minutes with a running water (flow rate: 5 liters / minute), and unreacted polyvinylamine was removed to obtain a final product.

After preparing two polypropylene films as final products obtained by the above method and applying an appropriate amount of adhesive on each side, the adhesive surfaces of the polypropylene film were bonded together, and the load was 1 kg / 10 cm ² ( Adhesive area width 25 mm × length 12.5 mm), cured at 25 ° C. and 65% RH for 3 days, and the tensile shear bond strength was measured according to JIS K 6850.
As the adhesive, a cyanoacrylate adhesive (manufactured by Toa Gosei Co., Ltd., trade name: Aron Alpha) was used.

(Example 5)
The final product obtained in the same manner as in Example 4 was pulled by the method described in Example 4 except that an epoxy resin adhesive (trade name: Bondquick 5 manufactured by Konishi Co., Ltd.) was applied as an adhesive. The shear bond strength was measured.

(Comparative Example 4)
The degreased polypropylene film was subjected only to plasma treatment under the conditions of Example 4 to obtain a final product, and the tensile shear bond strength of the obtained final product was measured by the method described in Example 4.

(Comparative Example 5)
The degreased polypropylene film was subjected only to plasma treatment under the conditions of Example 4 to obtain the final product, and the epoxy resin adhesive used in Example 5 was applied as an adhesive to the final product obtained. The tensile shear adhesive strength was measured in the same manner as in Example 4.

(Example 6)
A final product was obtained in the same manner as in Example 4 except that a 25 mm × 200 mm polypropylene film was used, and two obtained final products were obtained from a cyanoacrylate adhesive (product of Toa Gosei Co., Ltd., product). Name: Aron Alpha) is applied and bonded together, load is 1kg / 10cm ² (bonding area: width 25mm x length 15mm), cured at 25 ° C, 65% RH for 3 days, 180 ° peel adhesion The strength was measured according to JIS K 6854-2.

(Example 7)
The final product was obtained in the same manner as in Example 4 except that a 25 mm × 200 mm polypropylene film was used, and the adhesive was changed to an epoxy resin adhesive (trade name: Bondquick 5 manufactured by Konishi Co., Ltd.). Except for the above, the 180 ° peel adhesive strength of the final product obtained by the method described in Example 6 was measured.

(Comparative Example 6)
A degreased 25 mm × 200 mm polypropylene film is only subjected to plasma treatment under the conditions of Example 4 to obtain a final product, and the resulting final product has a 180 ° tensile shear bond strength by the method described in Example 6. It was measured.

(Comparative Example 7)
A degreased 25 mm × 200 mm polypropylene film was only subjected to plasma treatment under the conditions of Example 4 to obtain a final product. The resulting final product was obtained by using the epoxy resin adhesive used in Example 5 as an adhesive. The 180 ° tensile shear bond strength was measured by the method described in Example 6 except that it was used.

(Discussion)
In comparison between Example 5 and Comparative Example 5, the tensile shear bond strength was not observed because the polypropylene film itself as a base material was broken, but Example 4 was superior to Comparative Example 4. High value. Moreover, in the 180 ° peel adhesion strength, the values of Examples 6 and 7 are higher than those of Comparative Examples 6 and 7. Therefore, as a whole, it can be said that the secondary treatment with the polyamine compound or the polyimine compound after the plasma treatment improves the adhesion between the polypropylene film and the adhesive rather than the plasma treatment alone.
The reason for this is considered as follows.
By using a secondary treatment with a polyamine compound or a polyimine compound after the plasma treatment, many reaction sites of the polyamine compound or the polyimine compound are generated on the polypropylene film surface. A hydrogen bond, a polymerization reaction, or the like occurs between these reaction sites and the adhesive. As a result, the adhesion between the polypropylene film and the adhesive is improved as compared with the plasma treatment alone.

  As described above, according to the present invention, a general olefin resin can be used as a base material, and the dyeability, adhesiveness, hydrophilicity can be reduced by a gentle and simple process that does not adversely affect the characteristics of the base material. It is possible to provide a method for producing a surface-modified olefin resin capable of obtaining an olefin resin having excellent properties and paintability.

Claims (11)

  A method for producing a surface-modified olefin resin, comprising: activating an olefin resin, and bringing the olefin resin whose surface is activated by the activation treatment into contact with a polyamine compound and / or a polyimine compound.   After the activation treatment, when the surface tension of the activated olefin resin is 1.1 times or more than the surface tension of the olefin resin before the activation treatment, the activated olefin resin is added to the polyamine compound and 2. The method for producing a surface-modified olefin resin according to claim 1, wherein the surface-modified olefin resin is brought into contact with the polyimine compound.   The production method according to claim 1 or 2, wherein the polyamine compound and the polyimine compound have a weight average molecular weight of 1,000 to 200,000 (gel permeation chromatography method). The polyamine compound has a primary amine (R—NH ₂ ), a secondary amine (R ₂ —NH), a tertiary amine (R ₃ —N), or an amide (R—CONH ₂ ) in the molecule. The production method according to claim 3, which is a polymer or a copolymer (wherein R represents a hydrocarbon group selected from the group consisting of alkyl, aryl, aralkyl, alkenyl and alkynyl).   The manufacturing method according to any one of claims 1 to 4, wherein the olefin resin is polyethylene or a copolymer thereof, or polypropylene or a copolymer thereof.   A surface-modified olefin resin, characterized in that a polyamine compound is bonded to at least a part of a polyolefin via its amino group or amide group.   A surface-modified olefin resin, characterized in that a polyimine compound is bonded to at least a part of a polyolefin via its imino group.   The surface-modified olefin resin according to claim 6 or 7, wherein the polyamine compound or the polyimine compound has a weight average molecular weight of 1,000 to 200,000 (gel permeation chromatography method).   The polyolefin is an α-olefin homopolymer selected from the group consisting of ethylene, propylene, butene-1, pentene-2, hexene-1, 4-methyl-pentene-1, and octene-1, or these 2 The surface-modified olefin resin according to any one of claims 6 to 8, which is a copolymer of at least species, or a mixture of these homopolymers and / or copolymers.   The surface-modified olefin resin according to any one of claims 6 to 9, wherein the polyolefin is polyethylene or polypropylene, or a copolymer or a random copolymer of ethylene or propylene and another α-olefin.   The surface-modified olefin resin according to any one of claims 6 to 10, having a number average molecular weight of 10,000 to 500,000.