JPH04372640A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which, when used as a binder, gives a printing ink (esp. a special gravure ink) exhibiting sufficient adhesion to various plastic films and an excellent direct laminability. CONSTITUTION:A resin compsn. which comprises a polyurethane resin prepd. from polybutylene adipate having an average mol.wt. of 2,000, IPDI, 1,4- butanediol, and di-n-butylamine and a modified chlorinated polyolefin prepd. by reacting a low-mol.-wt. chlorinated polyolefin having carboxylic anhydride groups (e.g. 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. But, A
There is also a processing method (direct lamination) in which molten polypropylene or the like is directly laminated without using the C agent. Although the direct lamination method is economically advantageous, its suitability (adhesion) is mainly determined by the binder resin used in the printing ink. As binder resins conventionally used in printing inks, polyurethane resins having a wide range of adhesive properties to PET, NY, OPP, and other base films are generally used. In addition, chlorinated polyolefins such as chlorinated polypropylene are used as those having direct lamination suitability. [0003] However, printing inks using polyurethane resin as a binder have insufficient lamination suitability, especially direct lamination suitability, while inks using chlorinated polyolefin as a binder have insufficient suitability for lamination, especially direct lamination. It adheres well to OPP, but PET, NY
There is a problem that the base film that can be used is limited due to insufficient adhesion to. For this reason, resins made of polyurethane resin and chlorinated polyolefin have been proposed as a method of improving adhesion with various plastic films (for example, JP-A-61
255937). However, even these adhesives have insufficient adhesion. [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 polyurethane resin (A)
and a resin composition consisting of the following modified chlorinated polyolefin (B), "modified chlorinated polyolefin (B): chlorinated polyolefin (B1) having a carboxylic anhydride group,
A modified chlorinated polyolefin derived from a compound (B2) 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. ”. In the present invention, the polyurethane resin (A) is a polyol (a) and an organic diisocyanate (b).
Examples include polyurethane resins from Polyol (
Examples of a) include polyether diols, polyester diols and polyolefin diols. Examples of polyether diols include (1) alkylene oxide adducts of low molecular weight diols, and (2) ring-opened (co)polymers of cyclic ethers. Examples of low molecular weight diols in (2) 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-
hexane diol, 1,8-octamethylene diol,
[alkyl dialkanolamine, etc.], low molecular weight diols having a cyclic group [for example, those described in Japanese Patent Publication No. 4-1474], and mixtures of two or more of these. [0007]Alkylene oxides in (2) include alkylene oxides having 2 to 4 carbon atoms [ethylene oxide, propylene oxide, butylene oxide, etc.]
can be mentioned. [0008] As the ring-opening (co)polymer of (■), ring-opening polymerization or ring-opening copolymerization (block and/or random) of 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. [0010] 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. [0011] Examples of the low-molecular diol in (1) 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. When using these polyols (a), they can be used alone or in combination, but if oil resistance of printed matter is required, it is preferable to use polyester diol in an amount of 50% by weight or more. . These polyols (a
) average molecular weight (based on hydroxyl value measurement) is usually 500~
5000, preferably 700-4000. The organic diisocyanate (b) used in the present invention includes aliphatic diisocyanates having 2 to 12 carbon atoms (excluding carbon in the NCO group), and aliphatic diisocyanates having 4 to 1 carbon atoms.
5 alicyclic diisocyanates, aromatic aliphatic diisocyanates having 8 to 12 carbon atoms, aromatic diisocyanates having 6 to 20 carbon atoms, and modified products of these organic diisocyanates (carbodiimide groups, uretdione group, uretimine group, urea group, biuret group, and/or isocyanurate group-containing modified products). Examples of such organic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate (HDI).
, dodecamethylene diisocyanate, 1,6,11-
undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-isocyanatoethyl) fumarate, Bis(2-
Aliphatic diisocyanates such as isocyanate ethyl carbonate, 2-isocyanato ethyl 2,6-diisocyanate hexanoate; isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (water (added MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl) 4-
Alicyclic diisocyanates such as cyclohexene-1,2-dicarboxylate; xylylene diisocyanate,
Aroaliphatic disocyanates such as tetramethylxylylene diisocyanate and diethylbenzene diisocyanate
Tolylene diisocyanate (TDI), crude TDI
, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified MDI (carbodiimide modified MDI, etc.), aromatic diisocyanates such as naphthalene diisocyanate;
and mixtures of two or more thereof. Among these, preferred are aliphatic diisocyanates, cycloaliphatic diisocyanates and araliphatic diisocyanates. When producing the polyurethane resin (A), a chain extender (c) and a polymerization terminator (d) may be used if necessary. Examples of the chain extender (c) include low molecular weight diols and diamines having an average molecular weight of less than 500. As the low molecular diol, the above-mentioned polyester diol is used.
Diols and their alkylene oxide low molar adducts (molecular weight less than 500) are mentioned as raw materials for alcohols. Examples of diamines include aliphatic diamines (ethylenediamine, hexamethylenediamine, 1,2-propylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, etc.); Alicyclic diamines (isophorone diamine, 4,4'-dicyclohexylmethane diamine, isopropylidene dicyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, etc.), aromatic diamines (4,4'-diaminodiphenylmethane, etc.) , aromatic aliphatic diamines (such as xylene diamine), hydrazine, dihydrazide (such as adipic acid dihydrazide), and mixtures of two or more thereof. When using these (c), preferred are low molecular weight diols, alicyclic diamines, and combinations thereof. As the polymerization terminator (d), methyl alcohol is used.
Monohydric alcohols such as alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol; monoethylamine, n-propylamine, n-butylamine, -n-
Examples include alkyl monoamines such as propylamine and di-n-butylamine; hydroxyl monoamines such as monoethanolamine and diethanolamine. When these (d) are used, preferred are monohydric alcohols, alkyl monoamines, and combinations thereof. Examples of the method for producing polyurethane resin (A) include: (1) polyol (a), organic diisocyanate (b);
, a one-shot method in which chain extender (d) and polymerization terminator (c) are reacted together if necessary, or
) to create a urethane prepolymer having isocyanate groups at both ends, and react with a chain extender (c) and, if necessary, a polymerization terminator (d).It can be produced by any of the prepolymer methods. . Prepolymer method (2) is preferred from the viewpoint of ease of production. [0022] When producing the above urethane prepolymer in prepolymer method ①, organic diisocyanate (b
The equivalent ratio of isocyanate groups in ) to hydroxyl groups in polyol (a) is usually 1.1/1.0 to 5.0/1.0, preferably 1.2/1.0 to 3.0. /1.0. The total amount of the chain extender (c) and, if necessary, the polymerization terminator (d) used is substantially equivalent to the isocyanate group of the prepolymer, for example, the amount of the isocyanate group of the prepolymer per 1
The sum of the active hydrogen groups of the chain extender (c) and, if necessary, the polymerization terminator (d) relative to the equivalent weight is usually 0.95 to 1.05.
equivalent, preferably 0.98 to 1.02 equivalent. The molecular terminal of the polyurethane resin (A) may be any of an alkyl group, an NCO group, an OH group, or an NH2 group, but is preferably an alkyl group. [0023] Furthermore, the above methods (1) and (2) can be carried out in the presence or absence of a solvent. Usable solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, etc.), aromatic hydrocarbons (toluene, xylene, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), polyhydric alcohol derivatives (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), amides ( (dimethylformamide, etc.), sulfoxides (dimethylsulfoxide, etc.), and mixed solvents of two or more of these. Among these, preferred are acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate,
Propyl acetate, butyl acetate, tetrahydrofuran, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and mixed solvents of two or more of these be. The amount of solvent used is such that the weight ratio of the polyurethane resin (A) to the solvent is 100/0 to 10.
/90, preferably in the range of 80/20 to 20/80. The low molecular weight chlorinated polyolefin (B1) having a carboxylic anhydride group used in the present invention is as follows.
Examples include those obtained by reacting acid-modified polyolefin (i) with chlorine, and (ii) those obtained by reacting chlorinated polyolefin (i) with unsaturated polycarboxylic acid anhydride (ii). In (2), 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. [0027] In (2), to exemplify the method for producing acid-modified polyolefin, in an inert gas atmosphere, 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). The method for chlorinating this acid-modified polyolefin may be 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 ℃ (
B1) 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 5.
0%, 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 (B1)
) is preferably 0.5 to 30%, more preferably 1% to the weight of (B1) excluding chlorine atoms.
~20%. 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 (B2) of the present invention, the compound having a hydroxyl group includes monohydric alcohols (a1), dihydric alcohols (a2), polymer polyols (a3), polyoxy Examples include alkylene monools (a4) and acrylic polyols having a hydroxyl group (a5). 1
Examples of the alcohols (a1) include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylhexanol, Examples include stearyl alcohol and cyclohexanol. 2
As the alcohol (a2), polyurethane resin (
Examples include the low molecular weight diols mentioned in section A). Examples of the polymeric polyol (a3) include the polyether diols, polyester diols and polyolefin diols mentioned in the section of the polyurethane resin (A). Examples of the polyalkylene monool (a4) include those obtained by addition polymerizing an alkylene oxide to a monohydric alcohol. As the monohydric alcohol, those shown in the section (a1) 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, monohydric alcohols, dihydric alcohols, and polyether diols having a molecular weight of 100 to 10,000 are preferable.
polyester diol, condensed polyester diol, polyolefin diol
polyoxyalkylene monool and these two
It is a mixture of more than one species. More preferred are polyether diols, condensed polyester diols, polyolefin diols, polyoxyalkylene monols, and mixtures of two or more thereof, each having a molecular weight of 500 to 5,000. Examples of the compound having an amino group include diamines (b1) and dialkylamines (b2). Examples of the diamines (b1) include the diamines mentioned in the chain extender component in the section of the polyurethane resin (A), polyether diamine compounds (polyoxypropylene diamine, polyoxyethylene diamine, etc.), and the like. 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 an epoxy group include monoepoxies (butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, etc.), polyepoxies (polyethylene diglycidyl ether, polypropylene diglycidyl ether, glycidyl phenyl glycidyl ether, bisphenol A diglycidyl ether, etc.). Among these, monoepoxies and polyepoxies having a molecular weight of 100 to 5,000 are preferred. In producing (B), (B1) and (
The ratio between (B2) and (B1) can be changed in various ways.
The weight ratio with B2) is preferably (B1)/(B2)=
99/1 to 30/70, more preferably 95/5 to 5
It is 0/50. If (B2) is less than 1%, the compatibility with the polyurethane resin (A) decreases, and if it exceeds 70%, the lamination suitability decreases. Further, the equivalent ratio of the carboxylic anhydride group in (B1) and each functional group in (B2) is usually 1/0.
．． 1 to 1/2.0, preferably 1/0.2 to 1/1.5
It is. The production may be 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. Among the solvents listed in the section for polyurethane resin (A), those that are non-reactive with (B1) and (B2) can be used as the solvent. For example, aromatic hydrocarbons, esters, ketones, ethers, and two or more of these can be used. When (B2) is a compound having a hydroxyl group, (B1) and (B2) are mixed, and in the presence of a solvent, 50%
(B) is obtained by heating to ~150°C and reacting. Further, in the absence of a solvent, (B) can be obtained by heating to 100 to 200°C and reacting in a molten state. In the case where (B2) is a compound having an amino group, (B2) can be reacted in the same manner as in the case of a compound having a hydroxyl group.
) is obtained. In addition, in the case of a compound having an epoxy group, add an amine catalyst such as triethanolamine if necessary, and proceed as in the case of a compound having a hydroxyl group (
B) is obtained. [0041] In producing the resin composition of the present invention,
(2) (A) and (B) may be mixed, or (2) (A) and (B1) may be mixed and then (B2) is added and reacted. However, in the case of (1), (A) is used that has a structure that does not react with (B1). Specifically, a urethane resin free of hydroxyl groups, primary and secondary amino groups as functional groups is used. The resin composition of the present invention contains a polyurethane resin (A) and a modified chlorinated polyolefin (B) as essential components, but optionally unreacted (B1) and unreacted (B2). ), a solvent, etc. may be contained. The total weight of (A) and (B) in the resin solid content is usually 10 to 100% by weight, preferably 30 to 100% by weight.
%, more preferably 50 to 100%. If the total weight of (A) and (B) is less than 10%, the stability of the ink will decrease. The weight ratio of (A) and (B) is preferably (A
)/(B)=95/5 to 20/80, more preferably 90/10 to 30/70. If (B) is less than 5%, no improvement effect such as direct lamination suitability can be obtained, and if it exceeds 80%, the adhesiveness with PET or NY film will decrease. When the resin composition of the present invention is used as an ink binder, it can be used in the same manner as conventional ink binders (eg, polyurethane resins). That is, by blending the resin composition of the present invention with a pigment and, if necessary, other binder resins, solvents, and additives such as a pigment dispersant, and kneading the resin composition using ordinary ink manufacturing equipment such as a ball mill. Manufacture and use printing ink. Other resins mentioned above include polyamides, nitrocellulose, polyacrylates, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, chlorinated polyolefins, polystyrene, butadiene rubber, epoxy resins, and the like. An example of the formulation of a printing ink using the resin composition of the present invention is as follows (% indicates weight %). Resin composition of the present invention (per solid content)
10-20% pigment

5-40%
Other resins
0~10%
Solvents (including solvents in resin compositions)
40-75% additives

Appropriate Amount [0046]Although the resin composition of the present invention may be used for so-called one-component printing ink, it may also be used in combination with a polyisocyanate curing agent for two-component printing ink. You can also do it. 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; 1,6-hexamethylene diisocyanate or isophorone; Isocyanurate group-containing trimer synthesized by cyclic trimerization of the isocyanate group of diisocyanate; partial biuret reaction product synthesized from 1 mol of water and 3 mol of 1,6-hexamethylene diisocyanate, and mixtures of two or more thereof is suitable. The amount added is usually 0.5 to 10% by weight based on the ink. The printing method using a printing ink using the resin composition of the present invention as a binder may be the same as that for conventional special gravure inks. [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 %. (Production of polyurethane resin (A)) Production example 1 100 parts of polybutylene adipate (molecular weight 2000),
100 parts of poly-3-methylpentane adipate diol (molecular weight 2000), 12.6 parts of 1,4-butanediol
1 part, 55.5 parts of isophorone diisocyanate, 0.05 part of dioctyltin dilaurate, and 403 parts of toluene were charged into a reaction vessel, and reacted at 110°C for 8 hours. After cooling to 70°C, di-n-butylamine 1.
2 parts were added and the reaction was completed by further stirring for 1 hour to obtain a polyurethane resin solution (A-1) having a solid content of 40% and a viscosity of 45°C/25°C. Production Example 2 Polycaprolactone diol (molecular weight 2000) 200
A reaction vessel was charged with 7.2 parts of neopentyl glycol, 48.3 parts of isophorone diisocyanate, and 0.05 parts of dioctyltin dilaurate, and reacted at 100°C for 8 hours to obtain a urethane prepolymer with an NCO% of 1.55. Ta. Next, 388 parts of toluene was added and dissolved uniformly, and then a mixture of 6.7 parts of isophoronediamine, 3.1 parts of di-n-butylamine, and 10 parts of isopropanol was added to the toluene solution of the urethane prepolymer.
The reaction was carried out for 1 hour at .degree. C. to obtain a polyurethane resin solution (A-2) having a solid content of 40% and a viscosity of 52% at 25.degree. 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 9.5% by weight was obtained. 400 parts of this acid-modified polypropylene and 1,600 parts of carbon tetrachloride were charged into an apparatus 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 (b-1) with a combined chlorine content of 17% by weight. 300 parts of this (b-1) was dissolved in 577 parts of toluene to form polybutylene adipate (average molecular weight 2000) 8
Add 5 parts and react at 100℃ for 1 hour to reduce the solid content to 40%.
A modified chlorinated polypropylene (B-1) having a viscosity of 20°C/25°C was obtained. Next, the (A-
1) 200 copies and (B-1) 200 copies and MEK133
A uniform resin solution (I) having a solid content of 40% and a viscosity of 5.2% at 25° C. was obtained by stirring and mixing. Example 2 Acid-modified chlorinated polypropylene (b-
1) Dissolve 300 parts in 540 parts of toluene, add 60 parts of polypropylene glycol (average molecular weight 2000),
Reacted at 100℃ for 3 hours, solid content 40%, viscosity 20
Glass: Modified chlorinated polypropylene (B-
2) was obtained. Next, (A-1) 300 obtained in Production Example 1
100 parts of (B-2) and 133 parts of MEK were added and mixed with stirring to obtain a solid content of 30% and a viscosity of 3.0 viscosity/25.
A homogeneous resin solution (II) at .degree. C. was obtained. Example 3 Acid-modified chlorinated polypropylene (b-1) obtained in Example 1
300 parts and the polyurethane resin solution obtained in Production Example 2 (A
-2) Dissolve 600 parts in 540 parts of toluene, add 60 parts of polybutylene adipate (average molecular weight 2000),
React at 100°C for 1 hour, then add and dissolve 500 parts of MEK to obtain a solid content of 30% and a viscosity of 4.2% at 25°C.
A homogeneous resin solution (III) was obtained. Example 4 Acid-modified chlorinated polypropylene (b-1) obtained in Example 1
200 parts and the polyurethane resin solution obtained in Production Example 2 (A
-2) Dissolve 800 parts in 318 parts of toluene, add 12 parts of polyoxypropylenediamine (average molecular weight 600), react at 40°C for 1 hour, then add and dissolve 443 parts of MEK, solids content 30%. , viscosity 7.5 viscosity/2
A homogeneous resin solution (IV) at 5°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 Apply Nichiban Sellotape (12 mm width) to the printed surface, and rapidly pull one end of the Nichiban Sellotape 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, ×Poor. The results are shown in Table 1. Comparative Examples 1, 2, 3 As binder resins, only polyurethane resin (A-1), only acid anhydride group-containing chlorinated polypropylene (b-1), and 50 parts of (A-1) and (b- 1) Ink preparation, printing, and performance tests were conducted in the same manner as Test Examples 1 to 4 except that 50 parts of the mixture was used. The results are shown in Table 1. [Table 1] [Effects of the Invention] The resin composition of the present invention is useful as a binder for printing inks, and in particular, printing inks using the binder of the present invention can be used for 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, so it is possible to design inks for 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 applied as a paint primer or paint for various plastic molded products, such as interior and exterior parts of automobiles.

Claims (9)

[Claims] 1. A resin composition comprising a polyurethane resin (A) and the following modified chlorinated polyolefin (B). Modified chlorinated polyolefin (B): a low molecular weight chlorinated polyolefin (B1) having a carboxylic anhydride group and at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and an epoxy group in the molecule. Compound (B2
) and modified chlorinated polyolefins derived from. Claim 2: The weight ratio of (A) and (B) is 95/
The resin composition according to claim 1, which has a molecular weight of 5 to 20/80. Claim 3: The ratio of (B1) and (B2) is 9 in terms of weight ratio.
The resin composition according to claim 1 or 2, which has a molecular weight of 9/1 to 30/70. Claim 4: The content of chlorine atoms in (B1) is 5-5
The resin composition according to any one of claims 1 to 3, wherein the content is 0%. 5. The content weight of the carboxylic anhydride constituting (B1) is 0.0% relative to the weight of (B1) excluding chlorine atoms.
The resin composition according to any one of claims 1 to 4, which has a content of 5 to 30%. 6. (B2) is monohydric alcohol, dihydric alcohol, polyether diol, condensed polyester diol, polyolefin diol, polyoxyalkylene monool. The resin composition according to any one of claims 1 to 5, wherein the resin composition is one or more compounds selected from the group consisting of: and having a molecular weight of 100 to 10,000. 7. (B2) is selected from the group consisting of diamines and diacylamines, and has a molecular weight of 100 to 10
,000 compounds or more.
5. The resin composition according to any one of 5. 8. (B2) is selected from the group consisting of monoepoxies and polyepoxies, and has a molecular weight of 100 to 1.
Claim 1 is one or more than 0,000 compounds.
5. The resin composition according to any one of 5 to 5. (9) A binder for printing ink; (1) -
8. The resin composition according to any one of 8.