JPH04372641A - Binder comprising modified chlorinated polyolefin - Google Patents

Abstract

PURPOSE:To provide a binder which gives a printing ink (esp. a special gravure ink) exhibiting a sufficient adhesion to various plastic films and an excellent direct laminability. CONSTITUTION:A binder which comprises a modified chlorinated polyolefin resin prepd. by reacting a chlorination product of a maleic anhydride-modified polypropylene with polybutylene adipate (having an average mol.wt. of 2,000) in a solvent (toluene).

Description

Description: FIELD OF INDUSTRIAL APPLICATION This invention relates to a novel resin composition. In particular, the present invention relates to a resin composition useful as a binder for printing inks, paints or adhesives used for plastic films, sheets or molded articles. [0002] In recent years, with the diversification and high functionality of packaging materials, furniture, home appliances, automobile interior and exterior parts, etc., the materials used for these materials, such as plastic films, sheets, and molded products, have also become more attractive. There is a need for improvement. Furthermore, adhesives, printing inks, various coating agents, and the like used for these materials are required to have even higher performance. Among them, polyester film (PET), which is called flexible packaging, is
), nylon film (NY) or oriented polypropylene film (OPP), etc., in the production of packaging materials based on plastic films such as nylon film (NY) or stretched polypropylene film (OPP), film base materials are used to improve functionality such as heat sealability and airtightness. After printing using methods such as gravure printing or flexo printing,
Polyethylene films and unstretched polypropylene films are usually laminated by dry lamination or extrusion lamination. In particular, in extrusion lamination processing in which the material is coated with molten polyethylene or polypropylene, an anchor coating agent (AC agent) mainly composed of polyethyleneimine or polyisocyanate is usually used to provide adhesive strength to the ink layer. However, there is also a processing method (direct lamination) in which lamination is performed directly with molten polypropylene or the like without using an AC agent. The direct lamination method is economically advantageous. Conventionally, chlorinated polyolefins such as chlorinated polypropylene have been used as binder resins for printing inks that have direct lamination suitability (adhesion). [Problems to be Solved by the Invention] However, although ink using chlorinated polyolefin as a binder adheres well to OPP, it has insufficient adhesion to PET, NY, etc., so it cannot be used. There is a problem that the base film is limited. For this reason, the use of acid-modified chlorinated polyolefins has been proposed as a method of improving adhesion (for example, in JP-A-59-1665
Publication No. 34). However, even these materials do not have sufficient adhesion to various plastic films. [0004]Means for Solving the Problems The present inventors have developed a material that has sufficient adhesion to various plastic films and has good suitability for lamination by using it as a binder for printing ink. As a result of intensive studies aimed at obtaining a resin composition that can be used as a printing ink and also used as a paint binder, adhesive, etc., the present invention has been achieved. That is, the present invention provides a low molecular weight chlorinated polyolefin (A) having a carboxylic anhydride group, and a compound (B) having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and an epoxy group in its molecule. )
A binder characterized by comprising a modified chlorinated polyolefin (C) derived from. The low molecular weight chlorinated polyolefin (A) having a carboxylic anhydride group used in the present invention includes (i) polyolefin (i) and an unsaturated polycarboxylic anhydride (ii).
(1) A chlorinated acid-modified polyolefin obtained by reacting the following: [0006] In (1), the polyolefin (i) includes, for example, high density polyethylene, medium density polyethylene,
Low density polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, copolymer of ethylene and α-olefin, ethylene-propylene rubber, ethylene-
Propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, low-crystalline ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl ester copolymer, and combinations of two or more of these. Among these, polypropylene, propylene and α-
It is an olefin copolymer. The average molecular weight of polyolefin (i) is usually 1000 to 30000, preferably 2
000-25000. The polyolefin (i) may be obtained by degrading a high molecular weight polyolefin by thermal decomposition, and may also be obtained by a method of degrading a high molecular weight polyolefin by thermal decomposition, or by ordinary telomerization (α-
It may be obtained by copolymerizing olefins alone or by copolymerizing them. Examples of the unsaturated polycarboxylic anhydride (ii) include anhydrides of α,β-unsaturated polycarboxylic acids such as maleic anhydride, citraconic anhydride, and itaconic anhydride. [0008] In (2), to exemplify the method for producing acid-modified polyolefin, polyolefin (
i) in the presence or absence of aromatic and/or chlorinated solvents and with radical generating catalysts (peroxides such as di-tert-butyl peroxide, te
rt-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxide
oxide benzoate, etc., in the presence or absence of an azonitrile (e.g., azobisisobutyronitrile, azobisisovaleronitrile, azobisisopropionitrile, etc.), usually by heating and dissolving at 120°C to 220°C. An acid-modified polyolefin can be obtained by adding a saturated polycarboxylic anhydride in portions or all at once and reacting (graft polymerization). [0009] The acid-modified polyolefin may be chlorinated by any known method. For example, the acid-modified polyolefin is dissolved by heating in a chlorinated solvent such as carbon tetrachloride, and the
By blowing chlorine gas into the reaction at a temperature of ℃ (
A) can be obtained. In order to accelerate the reaction, the reaction may be carried out by irradiation with ultraviolet rays or under pressure. The combined chlorine content weight of the acid-modified chlorinated polyolefin is preferably 5 to 50
%, more preferably 10 to 35%. When it is less than 5% and more than 50%, adhesiveness decreases. The polyolefin (i) constituting the chlorinated polyolefin in (2) may be the same as those exemplified in (2). Further, the method for chlorinating this polyolefin (i) may be the same as the method exemplified in section (2). The unsaturated polycarboxylic acid anhydride (ii) may also be the same as those exemplified in the section (2). The method of reacting the chlorinated polyolefin (i) with the unsaturated polycarboxylic anhydride (ii) may be the same as the method exemplified in the section (2). Carboxylic anhydride (ii) constituting (A)
The content weight of (A) is preferably 0.5 to 30%, more preferably 1 to 2%, based on the weight of (A) excluding chlorine atoms.
It is 0%. If it is less than 0.5%, the adhesiveness with PET and NY films will decrease, and if it exceeds 30%, the adhesiveness with OPP film will decrease. In (B) of the present invention, the compounds having a hydroxyl group include monohydric alcohols (a1), dihydric alcohols (a2), polymer polyols (a3), polyoxy Examples include alkylene monools (a4) and acrylic polyols having a hydroxyl group (a5). Examples of monovalent alcohols (a1) include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2- Ethylhexano
alcohol, stearyl alcohol, cyclohexanol and the like. Examples of dihydric alcohols (a2) include aliphatic low molecular weight diols [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-, 1,3 -butanediol, neopentyl glycol, pentanediol, 3-methylpentanediol, 1,6-hexanediol, 1,8
-octamethylene diol, alkyl dialkanolamine, etc.], and low molecular weight diols having a cyclic group (for example, those described in Japanese Patent Publication No. 4-1474). Examples of the polymeric polyol (a3) include polyether diol, polyester diol and polyolefin diol. Examples of polyether diols include (1) alkylene oxide adducts of low molecular diols, and (2) ring-opened (co)polymers of cyclic ethers. [0015] Examples of the low-molecular diol in (2) include those shown in the section (a2). Examples of the alkylene oxide in (2) include alkylene oxides having 2 to 4 carbon atoms [ethylene oxide, propylene oxide, butylene oxide, etc.]. [0016] As the ring-opening (co)polymer of (■), ring-opening polymerization or ring-opening copolymerization (block and/or random) of the alkylene oxide and/or cyclic ether (tetrahydrofuran, etc.) exemplified in the section (■) can be used. Examples include those obtained by Specific examples of polyether diols include:
polyethylene glycol, polypropylene glycol,
Polyoxyethylene-polyoxypropylene diol (
block and/or random), polytetramethylene ether glycol, polytetramethylene ether
Examples include polyoxyethylene diol (block and/or random), polytetramethylene ether-polyoxypropylene diol (block and/or random), and mixtures of two or more thereof. As the polyester diol, (1) low molecular diol and/or polyester with a molecular weight of 1000 or less;
Examples include condensed polyester diol obtained by reacting terdiol with dicarboxylic acid and/or hydroxyl monocarboxylic acid, and polylactone diol obtained by ring-opening polymerization of lactone. [0019] Examples of the low-molecular diol in (2) include those exemplified in (2). Molecular weight in ■ 100
As the polyether diol of 0 or less, the above-mentioned polyether diol
Among the terdiols, those having a molecular weight of 1000 or less, such as polyethylene glycol, polytetramethylene ether glycol, polypropylene glycol, triethylene glycol, and mixtures of two or more thereof, can be mentioned. In addition, the dicarboxylic acids in (2) include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid,
glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), polymerized fatty acid dibasic acids (dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.), and mixtures of two or more of these. . Examples of the lactone in (2) include ε-caprolactone and δ-valerolactone. Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, and poly-3-methylpentane. adipate,
Polyethylene propylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate
polydiethylene adipate, poly(polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol -ol, polyvalerolactone diol, polycarbonate diol, and mixtures of two or more thereof. Examples of polyolefin diols include diols obtained by polymerizing butadiene and adding hydroxyl groups to both ends, and diols obtained by hydrogenating these diols. Specific examples of these polyolefin diols include polybutadiene diol, polyisoprene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol.
and mixtures of two or more thereof. Polyoxyalkylene monool (a4)
Examples include those obtained by addition polymerizing an alkylene oxide to a monohydric alcohol. As a monohydric alcohol (a
Those shown in section 1) can be used. Further, examples of the alkylene oxide include the alkylene oxides exemplified in the section (1). Acrylic polyol having hydroxyl group (a5
) includes a polymer obtained by reacting a monomer having a hydroxyl group and a radically reactive unsaturated double bond with one or more other copolymerizable monomers. Examples of monomers having hydroxyl groups include 2-hydroxylethyl (meth)acrylate and allyl alcohol; examples of copolymerizable monomers include alkyl (meth)acrylates [
Examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.], styrene, vinyl chloride, acrylonitrile, and the like. When these compounds having hydroxyl groups are used, they can be used alone or in combination. Among these, preferred are those having a molecular weight of 100 to 10,000;
Hydrolic alcohols, dihydric alcohols, polyether diols, condensed polyester diols, polyolefin diols, polyoxyalkylene monools, and mixtures of two or more of these. be. More preferred is a polyether di-
These include polyester diols, condensed polyester diols, polyolefin diols, polyoxyalkylene monools, and mixtures of two or more of these. Examples of the compound having an amino group include diamines (b1) and dialkylamines (b2). (b1) includes aliphatic diamines (ethylenediamine, hexamethylenediamine, 1,2-propylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, di-
2-hydroxyethylethylene diamine, etc.), alicyclic diamines (isophorone diamine, 4,4'-dicyclohexylmethane diamine, isopropylidene dicyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, etc.), aromatic diamines (4,4'-dicyclohexylmethane diamine, etc.), aromatic diamines (2-hydroxyethylethylenediamine, etc.), . Examples of (b2) include dibutylamine and di-2-ethylhexylamine. Among these, diamines and diacylamines having a molecular weight of 100 to 10,000 are preferred. More preferred are polyoxypropylene diamine and polyoxyethylene diamine having a molecular weight of 500 to 5,000. Examples of compounds having epoxy groups include monoepoxies (c1) and polyepoxies (c2). Examples of (c1) include butylglycidyl ether and phenylglycidyl ether. Examples of (c2) include polyethylene diglycidyl ether, polypropylene diglycidyl ether, glycidylphenylglycidyl ether, bisphenol A diglycidyl ether, and the like. Among these, monoepoxies and polyepoxies having a molecular weight of 100 to 10,000 are preferred. In producing (C), (A) and (B
) can be varied, and the weight ratio of (A) and (B) is preferably (A)/(B) = 99/1 to 3.
0/70, more preferably 95/5 to 50/50. If (B) is less than 1%, the adhesion to PET and NY films will decrease, and if it exceeds 70%, lamination suitability will decrease. The equivalent ratio of the carboxylic anhydride group in (A) to each functional group in (B) is usually 1/0.1 to 1/2.0, preferably 1/0.2 to 1/1. It is 5. The production is carried out in the presence or absence of a solvent, but the presence of a solvent is preferred in order to carry out a uniform reaction. As the solvent, a solvent that is non-reactive with (A) and (B) can be used. For example, ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents (ethyl acetate, propyl acetate, butyl acetate, etc.), ether solvents (tetrahydrofuran, etc.),
Examples include aromatic hydrocarbon solvents (toluene, xylene, etc.), amide solvents (dimethylformamide, etc.), sulfoxide solvents (dimethylsulfoxide, etc.), and mixed solvents of two or more of these solvents. Among these, preferred are acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, toluene, xylene, and mixed solvents of two or more of these. The amount of solvent to be used is such that the weight ratio of resin solid content to solvent is in the range of 100/0 to 10/90, preferably 80/20 to 20/80. When (B) is a compound having a hydroxyl group,
(A) and (B) are mixed, and in the presence of a solvent, 50 to 15
(C) is obtained by heating to 0°C and reacting. Further, in the absence of a solvent, (C) can be obtained by heating to 100 to 200°C and reacting in a molten state. (B)
When is a compound having an amino group, (C) can be obtained by reacting in the same manner as in the case of a compound having a hydroxyl group. In the case of a compound having an epoxy group, (C) can be obtained in the same manner as in the case of a compound having a hydroxyl group, by adding an amine catalyst such as triethanolamine if necessary. The binder of the present invention contains modified chlorinated polyolefin (C) as an essential component, but may also contain unreacted (A), unreacted (B), a solvent, etc. as optional components. You can. The content weight of (C) per solid content in the binder is usually 10 to 100%, preferably 3
It is 0 to 100%, more preferably 50 to 100%. If the weight content of (C) is less than 10%, adhesiveness decreases. The amount of solvent to be used is such that the weight ratio of solid content in the binder to solvent is 100/0 to 10/90, preferably 80/20 to
The amount is in the range of 20/80. When the binder of the present invention is used as an ink binder, it can be used in the same manner as conventional ink binders (for example, chlorinated polypropylene). That is, the binder of the present invention is blended with a pigment and, if necessary, other binder resins, solvents, pigment dispersants, and other additives, and the mixture is kneaded using ordinary ink manufacturing equipment such as a ball mill to print. Manufacture and use ink. Other binder resins mentioned above include polyurethane, polyamide, nitrocellulose, polyacrylates, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, chlorinated polyolefins, polystyrene, butadiene rubber, and epoxy resins. Can be mentioned. An example of the formulation of a printing ink using the binder of the present invention is as follows (% indicates weight %). Binder of the present invention (per solid content)
10-20% pigment

5-40%
Other binder resins
0-20% Solvent (including solvent in binder) 40
~75% additives

[0034]Although the binder of the present invention may be used for so-called one-component printing inks, it can also be used in combination with a polyisocyanate curing agent for two-component printing inks. can. In this case, the polyisocyanate curing agent is, for example, an adduct synthesized from 1 mole of trimethylolpropane and 3 moles of 1,6-hexamethylene diisocyanate, tolylene diisocyanate or isophorone diisocyanate;
Isocyanurate group-containing trimer synthesized by cyclic trimerization of isocyanate groups of , 6-hexamethylene diisocyanate or isophorone diisocyanate; partial biuret reaction product synthesized from 1 mole of water and 3 moles of 1,6-hexamethylene diisocyanate and mixtures of two or more of these are preferred. The amount added is usually 0.5 to 10% by weight based on the ink. The printing method using the printing ink using the binder of the present invention may be the same as that for conventional special gravure ink. [Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. In Examples, Production Examples, and Comparative Examples, "part" indicates part by weight, and "%" indicates weight %. Example 1 High molecular weight polypropylene (average molecular weight 125,000)
500 parts of polypropylene with an average molecular weight of 4000 obtained by thermal decomposition of
After raising the temperature to 0°C and dissolving it uniformly, 27 parts of dicumyl peroxide was added over 3 hours, and the reaction was continued for an additional 4 hours, and then xylene and unreacted maleic anhydride were distilled off under reduced pressure. Acid-modified polypropylene with a content of 9.0% by weight was obtained. 400 parts of this acid-modified polypropylene and 1,600 parts of carbon tetrachloride were charged into a device equipped with a reflux tube, and heated to 65 to 70°C.
After uniformly dissolving the mixture by heating, 70 parts of chlorine gas per hour was introduced into the reaction solution for 3 hours. After chlorination, residual chlorine and carbon tetrachloride in the reaction solution were distilled off under reduced pressure to obtain acid-modified chlorinated polypropylene (A-1) with a combined chlorine content of 17% by weight. 300 parts of this (A-1) was dissolved in 577 parts of toluene, and 8 parts of polybutylene adipate (average molecular weight 2000) was dissolved.
Add 5 parts and react at 100℃ for 1 hour to reduce the solid content to 40%.
A uniform modified chlorinated polypropylene solution (I) having a viscosity of 20°C/25°C was obtained. Example 2 Acid-modified chlorinated polypropylene (A-
1) Dissolve 300 parts in 540 parts of toluene, add 60 parts of polypropylene glycol, and react at 100°C for 3 hours to obtain a uniform modified chlorinated polypropylene solution (solid content 40%, viscosity 20°C/25°C). II) was obtained. Example 3 High molecular weight polypropylene (average molecular weight 125,000)
500 parts of polypropylene with an average molecular weight of 10,000 obtained by thermally decomposing the polypropylene and 30 parts of maleic anhydride were placed in a device equipped with a reflux tube, and 1,100 parts of xylene was added.
After raising the temperature to 50°C and dissolving it uniformly, 27 parts of dicumyl peroxide was added over 3 hours, and the reaction was continued for an additional 4 hours, and then xylene and unreacted maleic anhydride were distilled off under reduced pressure. Acid-modified polypropylene containing 5.3% by weight was obtained. 400 parts of this acid-modified polypropylene and 1,600 parts of carbon tetrachloride were charged into a device equipped with a reflux tube, heated to 65 to 70°C to uniformly dissolve them, and then
70 parts of chlorine gas per hour was introduced into the reaction solution for 6 hours. After chlorination, residual chlorine and carbon tetrachloride in the reaction solution were distilled off under reduced pressure to obtain acid-modified chlorinated polypropylene (A-2) with a combined chlorine content of 30% by weight. This (A-2) 30
0 part was dissolved in 480 parts of toluene, 20 parts of polyoxypropylene diamine (average molecular weight 600) was added, and the mixture was heated at 50°C.
A homogeneous modified chlorinated polypropylene solution (II
I) was obtained. Example 4 Acid-modified chlorinated polypropylene (A-2) obtained in Example 3
300 parts were dissolved in 540 parts of toluene, 60 parts of bisphenol A diglycidyl ether and 0.5 parts of triethanolamine were added, and after reacting at 100°C for 4 hours, the solid content was 40% and the viscosity was 40%/25%. A uniform modified chlorinated polypropylene solution (IV) at a temperature of 0.degree. C. was obtained. Test Examples 1 to 4 Printing inks were prepared using the resin solutions (I) to (IV) obtained in Examples 1 to 4 as binder solutions according to the following formulations. The above materials were placed in a steel can with an internal volume of 500 ml and kneaded for 1 hour using a paint conditioner (manufactured by Red Devil Co., Ltd.) to prepare an ink. Using the obtained printing ink, a polyester film (PE
T), printed on nylon film (NY) and oriented polypropylene film (OPP). The following performance tests were conducted on the obtained printed matter. (Performance test items and test methods) (1) Adhesive Nichiban Sellotape (12 mm width) is applied to the printed surface, and one end of the Nichiban Sellotape is rapidly pulled in a direction perpendicular to the printed surface. The state of the printed surface was observed when it was removed. (2) Blocking resistance Printed and non-printed surfaces are overlapped at a temperature of 40°C and a humidity of 60%.
A load of 1.0 Kg/cm2 was applied in RH, and after 24 hours, it was peeled off and the surface condition was observed. (3) Oil resistance After immersing the printed matter in rapeseed oil at 25° C. for 24 hours, the surface condition was observed. (4) Glue an untreated low-density polyethylene film onto the OPP print suitable for direct lamination, and use a heat sealer (manufactured by Toyo Seiki Co., Ltd.) for 20 minutes.
Hot melt pressure bonding was carried out at 0° C. x 1 KG/cm 2 , and T-peel strength was measured one day later. The criteria for determining each test result are: ◎Very good, ○Good, △Slightly poor, and ×Poor. The results are shown in Table 1. Comparative Examples 1 and 2 Except for using only acid anhydride group-containing chlorinated polypropylene resin (A-1) and chlorinated polypropylene (Toyo Kasei Kogyo Harden 15L chlorine content 30%) as the binder resin. Preparation of ink in the same manner as Test Examples 1 to 4,
Printing and performance tests were conducted. The results are shown in Table 1. [Table 1] [Effects of the Invention] The binder of the present invention is useful as a binder for printing inks, and in particular, the printing ink using the binder of the present invention can be applied to polyolefin films,
It has excellent properties such as good adhesion to a wide range of plastic films such as polyester films and nylon films, and suitability for direct lamination, making it possible to design inks that suit a wide range of purposes compared to conventional binder resins. . Furthermore, since the binder of the present invention has excellent adhesive properties to various plastics,
It can also be used as a paint primer or paint for various plastic molded products, such as interior and exterior parts of automobiles.

Claims (7)

[Claims] Claim 1: A low molecular weight chlorinated polyolefin (A) having a carboxylic anhydride group, and a compound (B) having at least one functional group selected from the group consisting of a hydroxyl group, an amino group and an epoxy group in the molecule. ) A binder comprising a modified chlorinated polyolefin (C) derived from Claim 2: The weight ratio of (A) and (B) is 99/
2. The binder according to claim 1, wherein the binder has a molecular weight of 1 to 30/70. Claim 3: The weight of chlorine atoms contained in (A) is 5 to 50.
% of the binder according to claim 1 or 2.
. [Claim 4] The content weight of the carboxylic anhydride constituting (A) is 0.5 to 0.5 to the weight of (A) excluding chlorine atoms.
The binder according to any one of claims 1 to 3, wherein the binder content is 30%.
. Claim 5: (B) is a monohydric alcohol, a dihydric alcohol
One compound selected from the group consisting of polyester diols, polyether diols, condensed polyester diols, polyolefin diols, and polyoxyalkylene monools, and having a molecular weight of 100 to 10,000. or 2 or more kinds of binders according to any one of claims 1 to 4. 6. (B) is selected from the group consisting of diamines and diacylamines, and has a molecular weight of 100 to 10,
Claims 1 to 4 are one or more types of compounds of 000.
The binder according to any one of the above. 7. (B) is selected from the group consisting of monoepoxies and polyepoxies, and has a molecular weight of 100 to 10
,000 compounds or more.
4. The binder according to any one of 4.