JPH05194926A - Binder resin composition and its production - Google Patents

Abstract

PURPOSE:To prepare the subject compsn. giving a coating material, a printing ink, or an adhesive which exhibits excellent properties when applied to a plastic film. sheet, or molding. CONSTITUTION:The objective compsn. which gives a transparent and homogeneous soln. is prepd. by grafting 80-20wt.% radical-polymerizable monomer onto 20-80wt.% degraded amorphous polyolefin comprising propylene, ethylene, and another alpha-olefin under such conditions that the polyolefin is dissolved in an org. solvent in a concn. of 20-50wt.%; that after an org. peroxide is added to the polyolefin soln., the monomer is added slowly in such a way that its concn. in the reaction liq. does not exceed 0.5mol/l; that at least 50mol% of the monomer is a 4-12C acrylic ester; and that the reaction is carried out at a temp. where the half life of the peroxide is 3-5hr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder resin composition used for the purpose of protecting various plastics, cosmetics and adhesion, and more specifically, a polyolefin resin, a polyurethane resin, a polyamide resin, an acrylic resin, The present invention relates to a binder resin composition for paints, printing inks, or adhesives, which exhibits excellent physical properties for films, sheets or molded products of various synthetic resins such as polyester resins.

[0002]

2. Description of the Related Art Plastic is highly productive, has a high degree of freedom in design, and is lightweight.
Since it has many advantages such as rust prevention and impact resistance, it has been widely used in recent years as a material for automobile parts, electric parts, building materials and the like. In particular, polyolefin resins are widely used as industrial materials because they have many excellent properties such as low cost, moldability, chemical resistance, heat resistance, water resistance, and good electrical properties. Growth is one of the most anticipated materials.

However, unlike a synthetic resin having a polarity, such as a polyurethane resin, a polyamide resin, an acrylic resin, a polyester resin, a polyolefin resin is non-polar and crystalline, so that it is difficult to coat or bond it. There is a drawback to say. Therefore, conventionally, the surface of the polyolefin resin molded product is improved by adhering it by plasma treatment or gas flame treatment to improve the adhesion, but this method is complicated and requires a large amount of equipment cost and time loss. In addition, there is a drawback that the surface treatment effect varies due to the complexity of the shape of the molded product and the influence of pigments and additives in the resin.

As a method of coating without such a pretreatment, various primer compositions such as those used for coating polypropylene bumpers for automobiles have been proposed. For example, Japanese Patent Publication No. 62-21027 proposes a surface treating agent obtained by modifying a propylene-α-olefin copolymer with maleic acid. However, a primer composition obtained by simply introducing maleic acid into a polyolefin has the drawbacks of poor sprayability, solubility, and compatibility, although it has adhesion and solvent resistance. In addition, it is complicated with a two-coat finish.

As a coating composition for a one-coat finish, there are chlorinated polyolefins and cyclized rubbers having a strong adhesive force to a polyolefin resin, but weather resistance,
Moisture resistance, gasoline resistance, etc. are inferior and do not show sufficient coating film performance. Therefore, attempts have been made to mix and use acrylic resins and alkyd resins having good paint properties, but originally acrylic resins and alkyd resins have poor compatibility with chlorinated polyolefins, which reduces the gloss of the coating film, This causes problems such as a marked loss of appearance.

In order to improve these drawbacks, Japanese Patent Laid-Open No.
No. 71996, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin, and an acrylic resin having a hydroxyl group, as shown in JP-A-59-27968. A coating composition comprising a chlorinated polyolefin-modified hydroxy group-containing acrylic copolymer obtained by copolymerizing a monomer and the like with a chlorinated polyolefin and an isocyanate compound as essential components, and JP-A-62-9537.
Adhesive comprising a hydroxyl group-containing acryl-modified chlorinated polyolefin copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber and an isocyanate compound as main components, as seen in JP-A-2 Resin compositions and the like have been proposed. However, these chlorine-containing compositions are slightly inferior in ultraviolet resistance and heat resistance and have a problem in long-term weather resistance.

A composition containing no chlorine is disclosed in Japanese Patent Laid-Open No.
JP-A-2-27308 proposes a method for forming a multilayer coating film comprising a cross-linking agent and a resin composition obtained by copolymerizing a polyolefin graft-polymerized with maleic acid, a functional group monomer and a radically polymerizable unsaturated monomer. .. In addition, a method of introducing an unsaturated bond into polyolefin (JP-A-1-123812 and JP-A-2-269109) and a method of introducing an organic peroxide (JP-A-1-13).
No. 1220), a method using a bifunctional organic peroxide (Japanese Patent Laid-Open No. 64-36614) and the like have been proposed, but all of them improve the reactivity of the polyolefin with the radically polymerizable unsaturated monomer. It is a device for making it happen.

However, in these methods, when the copolymerization reaction is carried out at a high concentration, gelation may occur during the reaction, and therefore it is necessary to carry out the reaction at a very dilute concentration. For this reason, the graft copolymerization efficiency to polyolefin is very low, a homopolymer of a radically polymerizable unsaturated monomer is likely to be formed, and two layers are separated unless a step such as refining is performed, so that it cannot be used as it is.

On the other hand, various kinds of plastic films have been developed and used as food packaging materials.
Along with this, packaging forms have been diversified, and in particular, in order to protect packaging contents, the use of laminated composite films is increasing. As the laminating ink used for these packaging, a large number of inks are properly used depending on the type of film, but today, the laminating ink is roughly classified into two types. That is, an ink composition mainly composed of chlorinated polypropylene and chlorinated ethylene vinyl acetate copolymer mainly used for polypropylene film, and an ink composition mainly composed of polyester resin and urethane resin mainly used for nylon film. ..

The former ink composition containing a chlorinated polypropylene and a chlorinated ethylene vinyl acetate copolymer as a main binder is disclosed, for example, in JP-B-60-31670.
An ink composition obtained by further converting a chlorinated ethylene vinyl acetate copolymer into a sulfochlorate is disclosed in JP-A-55-14577.
No. 5 publication. These have good ink adhesion to the untreated polypropylene film, and also show good adhesion when laminated printed by the extrusion lamination method. However, it has poor adhesion to films of polyester, nylon and the like, and is not suitable as a printing ink for lamination to these films.

The latter ink composition containing a urethane resin as a main binder is a film having polarity such as polyester and nylon as disclosed in JP-A-62-153366 and JP-A-62-153367. However, it does not adhere to untreated polypropylene film at all, and printing by the polypropylene extrusion lamination method is impossible.

[0012]

DISCLOSURE OF THE INVENTION As described above, the present invention is free from the deterioration of weather resistance found in chlorinated polyolefin binder resins, and the crosslinking and gel found in conventional non-chlorine polyolefin graft products. Homogeneous solution with less physical properties and adhesion to polyolefins and excellent properties for films, sheets or molded products of various synthetic resins such as polyurethane resins, polyamide resins, acrylic resins, polyester resins, etc. An object of the present invention is to provide a binder resin composition for paints, printing inks, or adhesives having good transparency.

The present inventors have already disclosed in Japanese Patent Laid-Open No. 61-215.
In Japanese Patent No. 666, regarding the graft polymerization of an acrylic monomer onto a chlorinated polyolefin and a chlorinated polydiene, the invention has been completed and its effect has been confirmed as a binder that adheres to both the polyolefin and other polar resins. However, it was found that deterioration due to desorption of hydrochloric acid becomes a problem when higher performance is required or when it is used for a long period of time.

Therefore, the inventors of the present invention used, as an organic peroxide, a polyolefin obtained by copolymerizing propylene, which is a polyolefin that is not chlorinated but has good solubility in a solvent, with ethylene, and an α-olefin having 4 to 20 carbon atoms. After degrading by heat, the method of graft-polymerizing the radical-polymerizable monomer was studied and various studies were conducted. As a result, it was found that a uniform graft polymer can be obtained under the following conditions.

That is, according to the present invention, a polyolefin obtained by randomly copolymerizing propylene, ethylene and an α-olefin having a carbon number of 4 to 20 by organic peroxide and / or heat degrading is added to a radical of 20 to 80% by weight. When 80 to 20% by weight of a polymerizable monomer is added to perform graft polymerization, each of the following requirements (a), (b), (c), and (d): (a) Polyolefin in an organic solvent having a solid content concentration of 20 to
It dissolves in the range of 50% by weight, and (b) after adding an organic peroxide to the polyolefin solution, the unsaturated carboxylic acid derivative is gradually added within a range such that the concentration in the reaction solution does not exceed 0.5 mol per liter. At a temperature at which (c) at least 50 mol% of the radical-polymerizable monomer is an acrylate ester having 4 to 12 carbon atoms, and (d) the organic peroxide has a half-life of 3 to 5 hours. Do the reaction, either 1
, Any two, any three or all of them, and a binder resin composition having good uniform transparency of a resin solution, a method for producing the same, and a binder resin for paints, inks and adhesives using the same It is a composition.

Here, propylene, ethylene and carbon number 4
The polyolefin obtained by copolymerizing .alpha.-olefin of .about.20 is preferably a random copolymer, and the amount ratio of propylene, ethylene and .alpha.-olefin can be selected if necessary. In particular, when adhesion to polypropylene is required, it is desirable that the content of propylene component is 50 mol% or more.

As the α-olefin having 4 to 20 carbon atoms, butene-1, pentene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-
1, octene-1, nonene-1, decene-1, dodecene-1 and the like, particularly those having 4 to 10 carbon atoms are preferable.

Degradation of the polyolefin may be carried out by a conventionally performed method in a hot-melt state, and is carried out by only heat and / or by a degradation reaction in which an organic peroxide is added. The temperature at this time is 120-250
The temperature may be in the range of ° C, and as the organic peroxide, di-cumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, t-butyl peroxyacetate or the like can be used. The molecular weight of the polyolefin after degradation can be adjusted as necessary, but from the viewpoint of solubility, it is preferably about 1 to 30,000.

By using the random copolymerized polyolefin thus degraded, there is no deterioration of the resin due to the elimination of chlorine found in the modified product using the chlorinated polyolefin, and the physical properties such as ultraviolet resistance and heat resistance are improved. Can be expected to improve.

As the radically polymerizable monomer used in the graft polymerization, unsaturated monocarboxylic acid ester and unsaturated dicarboxylic acid ester or acid anhydride, unsaturated aromatic monomer, and the like can be used. As the unsaturated monocarboxylic acid ester, an acrylic acid ester having 4 to 20 carbon atoms, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, cyclohexyl acrylate, and / or methacrylic acid esters, such as methyl methacrylate, ethyl methacrylate, Propyl methacrylate, n-butyl methacrylate, methacrylic acid, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate. Meta 2-hydroxyethyl acrylate, methacrylic acid 2-hydroxypropyl, there is meta-cyclohexyl acrylate and the like.

As the unsaturated dicarboxylic acid derivative, maleic anhydride, dimethyl maleate, diethyl maleate, di-2-ethylhexyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, di-2-fumarate. Examples thereof include ethylhexyl and dibutyl fumarate.

Further, as the unsaturated aromatic monomer, styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, α-methylstyrene, α-
Ethyl styrene etc. are mentioned. Other radically polymerizable monomers include vinyl acetate, vinyl propionate, acrylonitrile, acrylamide and the like.

The present invention is an effective method when the radical polymerizable monomer is added in an amount of 80 to 20% by weight with respect to the polyolefin in an amount of 20 to 80% by weight, and graft polymerization is carried out. The adhesiveness to various polar base materials such as polyurethane-based resins and polyester-based resins is deteriorated when it exceeds 80% by weight. Preferably polyolefin is 40-6
It is preferably in the range of 0%.

In the present invention, these radical-polymerizable monomers can be used alone or in combination of several kinds, but it is necessary that at least 50 mol% of them is an acrylate having 4 to 12 carbon atoms. However, if it is less than the above range, the polymerization reaction rate remarkably decreases, and it becomes difficult to maintain the concentration of the monomer in the reaction solution within the range not exceeding 0.5 mol per liter, and two-layer separation occurs. Further, an acrylic acid ester having more than 12 carbon atoms has a low polymerization rate and causes two-layer separation for the same reason as above.

Acrylic acid esters are preferable as the main component of the radical-polymerizable monomer because they give a better effect on the gloss and flexibility of the coating film when it is used as a paint or ink.

Examples of the acrylate ester include those having 4 to 12 carbon atoms among the above-mentioned ones, and cyclohexyl acrylate is preferably used especially for inks and paints requiring moisture resistance and solvent resistance. ..

These reactions are carried out in an organic solvent, and examples of the organic solvent used at this time include benzene, toluene, xylene, cyclohexane, methylcyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, tetrahydrofuran and the like.

The reaction concentration starts at a solid content of 20 to 50 wt% when only the polyolefin is dissolved, and an organic peroxide is added to the solid concentration, and then the radical-polymerizable monomer is added to the reaction liquid in the concentration. Is gradually added in such a range that does not exceed 0.5 mol per liter.

The initial reaction concentration is important for controlling the initial reaction of the grafting reaction, and it is carried out in the range of 20 to 50% by weight, but if it is lower than 20% by weight, the grafting efficiency decreases.
Layer separation occurs, and if it is higher than 50% by weight, there is a tendency that cross-linking or gelation occurs and the viscosity rises.

The radical-polymerizable monomer is added gradually within a range such that the concentration in the reaction solution does not exceed 0.5 mol per liter, but the radical-polymerizable monomer may be added depending on the polymerization reactivity of the radical-polymerizable monomer used. It is important to adjust the addition rate so that the addition rate is maintained within a range not exceeding the monomer consumption rate. When the concentration of the radical-polymerizable monomer exceeds 0.5 mol per liter, the homopolymer of the radical-polymerizable monomer is remarkably produced and grown, and two layers are separated. The concentration of unreacted radical-polymerizable monomer can be quantified by gas chromatography or the like.

The reaction temperature is such that the half-life of the organic peroxide used is 3 to 5 hours, but if it is shorter than 3 hours, the self-polymerization of the radical-polymerizable monomer will be promoted and a homopolymer will be formed to form two layers. Separation occurs or cross-linking between polymer molecules occurs, and a gelled product is easily generated. If it is longer than 5 hours, the polymerization reaction is difficult to proceed and sufficient graft polymerization tends to be inhibited. The binder resin composition solution obtained by the production method of the present invention is a solution having good uniform transparency at a practical concentration, and a coating film obtained by casting this on a film or the like is also uniform and transparent.

The binder resin composition of the present invention can be coated as it is by simply adjusting the concentration of the reaction solution, but it is also used as a pigment, solvent, pigment dispersant, viscosity modifier, plasticizer, stabilizer, crosslinking curing agent. It can also be used as an ink, a paint or an adhesive by adding the above ingredients and kneading. In addition, alkyd resin, acrylic resin, polyester resin, polyether resin, polyurethane resin,
Polyolefin, chlorinated polyolefin, etc. may be added and used.

[0033]

The present invention has no deterioration in weather resistance found in chlorinated polyolefin-based binder resins, has less cross-linking or gelation found in conventional non-chlorine polyolefin-based graft products, and has adhesiveness to polyolefin, And films of various synthetic resins such as polyurethane resins, polyamide resins, acrylic resins, polyester resins,
It is an object of the present invention to provide a binder resin composition for paints, printing inks, or adhesives, which shows excellent physical properties for sheets or molded products.

In order to achieve this purpose, we have:
It was possible to obtain a homogeneous and transparent binder resin composition solution by optimizing the graft reaction conditions by the conventional radical polymerization using a degraded product of a random copolymerized polyolefin containing no chlorine in the polyolefin.

In the grafting reaction by radical polymerization, the following is generally known as a method for improving the grafting efficiency. (By Fumio Ide, Graft and its application
Polymer Society) 1) Higher trunk polymer concentration is better 2) Lower monomer concentration is better 3) Radical generator concentration is better

However, it is actually very difficult to select a combination that satisfies such conditions, and a combination that imparts practical physical properties to this is not easily obtained. .. Further, since the main use of the conventional graft-polymerized product of a radical-polymerizable monomer to a polyolefin was a modifier for a plastic molded product, its homogeneity can be achieved by using a solution and a dry solution as obtained in the method of the present invention. At present, the coating film does not have perfect uniform transparency.

Therefore, the inventors of the present invention investigated a combination of conditions that satisfied the physical properties in coating and ink applications and obtained a more uniform graft polymer, and found that not only the graft efficiency was increased but also during the reaction. As a result of studying how to compatibilize the homopolymer of the acrylic resin which is inevitably formed, the present invention has been completed by the following idea.

First, the degraded random copolymerized polyolefin was used to improve the solubility of the polyolefin and to lower the molecular weight thereof, thereby improving the compatibility with the homopolymer of the acrylic resin. In addition, a carbon-carbon double bond was introduced at the molecular end by the degradation reaction to improve the reactivity of the polyolefin itself. The initial concentration of the trunk polymer can be increased by gradually adding the radical-reactive monomer to the solution in which this is dissolved.

Furthermore, by gradually adding the monomer, it was possible to keep the monomer concentration below a certain value, and it was also possible to maintain a high trunk polymer concentration relative to the monomer. Further, by maintaining the monomer concentration low, it is possible to suppress the molecular weight of the homopolymer or graft chain produced, and it is expected that the compatibility between the polyolefin and the acrylic resin can be improved.

Acrylic acid ester having 4 to 12 carbon atoms is used for at least 50 mol% of the radical-polymerizable monomer to be graft-polymerized, which is suitable for pigments used in paints and inks. It is a choice to obtain necessary physical properties such as having dispersion performance,
This is because a methacrylic acid ester or an acrylic acid ester having a carbon number of 12 or more has a slow polymerization rate, so that the monomer concentration becomes high and sufficient graft polymerization does not easily proceed.

Further, the easiness of graft polymerization on a polyolefin is in the order of unsaturated dicarboxylic acid derivative> acrylic acid ester> methacrylic acid ester. However, unsaturated dicarboxylic acid derivatives are short grafts because the growth reaction of graft chains does not easily occur. Since only chains are formed, it is expected that the effect of compatibilizing the homopolymer of the radical-polymerizable monomer formed during the reaction will be small. Therefore, it is considered that a stable graft reaction can easily proceed by using as the main component an acrylic acid ester having 4 to 12 carbon atoms in which the growth reactivity of the molecular chain and the graftability to the polyolefin are well balanced.

[0042]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 In a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel, a polyolefin which is a random copolymer of propylene, ethylene and butene (propylene component 75 mol%, ethylene component 20 mol%, 1-butene component 5 mol%, molecular weight 90,000) was dissolved at around 200 ° C., and 100 parts by weight of a denatured polyolefin having a molecular weight of 30,000 was dissolved in 230 parts by weight of toluene, and after heating at 105 ° C. 7 parts by weight of t-butyl peroxyisopropyl carbonate were added. (The half-life at this time is about 4 hours)

Stirring was continued while maintaining the temperature at 100 ° C., and a solution obtained by mixing 120 parts by weight of cyclohexyl acrylate, 10 parts by weight of dimethyl maleate, 20 parts by weight of 2-hydroxyethyl acrylate and 140 parts by weight of toluene was added thereto. Added by tube pump over 3 hours. The reaction was further continued for 4 hours with sufficient stirring and then cooled.

The resin solution obtained had a concentration of 40% and a concentration of 25%.
Solution viscosity at ℃ is 320 CPS, weight average molecular weight is 7
The residual monomer content was 0.1% or less.

Example-2 100 parts by weight of a degraded polyolefin having a molecular weight of 30,000 which was degraded in the same manner as in Example-1 in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel. Parts were dissolved in 230 parts by weight of toluene, and after heating to 105 ° C., t
-Butyl peroxyisopropyl carbonate 7 parts by weight were added. (The half-life at this time is about 4 hours)

Stirring was continued while maintaining the temperature at 100 ° C., and 90 parts by weight of cyclohexyl acrylate, 30 parts by weight of cyclohexyl methacrylate, 10 parts by weight of dimethyl maleate, 20 parts by weight of 2-hydroxyethyl acrylate and 140 parts of toluene. The solution mixed with parts by weight was added by a tube pump over 3 hours. The reaction was further continued for 4 hours with sufficient stirring and then cooled.

The concentration of the obtained resin solution was 40% and was 25
Solution viscosity at ℃ 540CPS, weight average molecular weight 6
The residual monomer content was 0.5%.

Example 3 In a four-necked flask equipped with a stirrer, a cooling pipe, a thermometer and a dropping funnel, 100 parts by weight of a degraded polyolefin having a molecular weight of 30,000 was degraded in the same manner as in Example-1. Was dissolved in 375 parts by weight of toluene, heated to 105 ° C., and then t-
7 parts by weight of butyl peroxyisopropyl carbonate were added. (The half-life at this time is about 4 hours)

Continue stirring while maintaining the temperature at 82 ° C.
90 parts by weight of cyclohexyl acrylate, 30 parts by weight of cyclohexyl methacrylate, 1 part of dimethyl maleate
0 parts by weight, and 2-hydroxyethyl acrylate 20
The solution mixed with parts by weight was added by a tube pump over 3 hours. The reaction is 4 with more thorough stirring.
After continuing for a time, it was cooled.

The concentration of the obtained resin solution was 40% and was 25
Solution viscosity at ℃ 250 CPS, weight average molecular weight 5
The residual monomer content was 0.5%.

Example 4 In a four-necked flask equipped with a stirrer, a cooling pipe, a thermometer and a dropping funnel, 100 parts by weight of a degraded polyolefin having a molecular weight of 30,000 was degraded in the same manner as in Example-1. Was dissolved in 230 parts by weight of toluene, heated to 82 ° C., and then 7 parts by weight of benzoyl peroxide was added (half-life at this time was about 4 hours).

Continue stirring while maintaining the temperature at 82 ° C.
A solution obtained by mixing 90 parts by weight of cyclohexyl acrylate, 30 parts by weight of 2-ethylhexyl methacrylate, 10 parts by weight of dimethyl maleate, 20 parts by weight of 2-hydroxyethyl acrylate and 140 parts by weight of toluene with a tube pump for 3 hours. Added. The reaction was further continued for 4 hours with sufficient stirring and then cooled.

The resin solution obtained had a concentration of 40% and a concentration of 25%.
Solution viscosity at ℃ is 180 CPS, weight average molecular weight is 6
The residual monomer content was 0.1%.

Example 5 100 parts by weight of a degraded polyolefin having a molecular weight of 30,000 and degraded in the same manner as in Example 1 in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel. Was dissolved in 250 parts by weight of toluene, heated to 82 ° C., and then 7 parts by weight of benzoyl peroxide was added. (The half-life at this time is about 4 hours)

Continue stirring while maintaining the temperature at 82 ° C.
A solution prepared by mixing 90 parts by weight of cyclohexyl acrylate, 30 parts by weight of 2-ethylhexyl methacrylate, 10 parts by weight of dimethyl maleate, and 20 parts by weight of 2-hydroxyethyl acrylate was added thereto by a tube pump over 3 hours. The reaction was further continued for 4 hours with sufficient stirring and then cooled.

The concentration of the obtained resin solution was 50% and was 25
The solution viscosity at 40 ° C. and 40% was 480 CPS, the weight average molecular weight was 100,000, and the residual monomer content was 0.1% or less.

Comparative Example-1 100 parts by weight of a degraded polyolefin having a molecular weight of 30,000 which was degraded in the same manner as in Example-1 in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel. Was dissolved in 230 parts by weight of toluene, heated to 105 ° C., and then t-
7 parts by weight of butyl peroxyisopropyl carbonate were added. (The half-life at this time is about 4 hours)

Stirring was continued while maintaining the temperature at 100 ° C., and 120 parts by weight of cyclohexyl methacrylate,
A solution obtained by mixing 10 parts by weight of dimethyl maleate, 20 parts by weight of 2-hydroxyethyl acrylate and 140 parts by weight of toluene was added by a tube pump over 3 hours. The reaction was further continued for 4 hours with sufficient stirring and then cooled.

The concentration of the obtained resin solution was 40% and was 25
Solution viscosity at ℃ is 180 CPS, weight average molecular weight is 4
The residual monomer was 2.1%. The solution was allowed to stand for 1 day and then separated into two layers.

Comparative Example-2 100 parts by weight of a degraded polyolefin having a molecular weight of 30,000 which was degraded in the same manner as in Example-1 in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel. Parts were dissolved in 250 parts by weight of toluene, and after heating to 110 ° C., t
-Butyl peroxyisopropyl carbonate 7 parts by weight were added. (The half-life at this time is about 2 hours)

Stirring was continued while maintaining the temperature at 107 ° C., and 90 parts by weight of cyclohexyl acrylate, 30 parts by weight of cyclohexyl methacrylate, 10 parts by weight of dimethyl maleate, and 20 parts by weight of 2-hydroxyethyl acrylate were mixed therein. The above solution was added by a tube pump in 3 hours. The reaction is 4 with more thorough stirring.
After continuing for a time, it was cooled.

The concentration of the obtained resin solution was 40% and was 25
Solution viscosity at ℃ 1800CPS, weight average molecular weight 2
The residual monomer content was 30,000 and 0.2%. The solution became cloudy during the reaction and separated into two layers.

Table 1 shows the reaction formulation and the physical properties at 25 ° C. of the binder solution in which the solid content concentration was adjusted to 40% by weight.

[0065]

[Table 1] The monomer concentration showed the maximum value during the reaction. A B type viscometer was used for the viscosity measurement.

From Table 1, it can be seen that in Examples 1 to 5 corresponding to the present invention, solutions having good transparency and having no two-layer separation were obtained. Further, it can be seen that these solutions are resin solutions in which the molecular weight and viscosity are appropriately adjusted and the amount of crosslinking and gelation is small.

Next, the performance when these binder resin compositions are applied to coating materials will be described with reference to formulation examples 1 and 2. Further, Reference Example 1 was shown with respect to the physical properties of the conventional chlorinated polyolefin resin.

Formulation Example-1 Binder resin solution (solid 4) obtained in Example-1
0%) 100 g and titanium dioxide 26 g in a sand mill
After kneading for an hour, isocyanate curing agent Desmodur Z4370 (manufactured by Sumitomo Bayer Urethane Co., isophorone diisocyanate system, isocyanurate body) 1
9.7 g was added, and No. 13 to 1 in 4 Ford Cup
The viscosity was adjusted with xylene so that the temperature was 5 seconds / 20 ° C. A polypropylene plate, TX-933A (manufactured by Mitsubishi Petrochemical Co., Ltd.) was spray-painted. After drying at room temperature for 15 minutes,
The coating film was tested by forced drying at 80 ° C. for 30 minutes and leaving it in the room for 1 week. The results are shown in Table 2.

Formulation Example-2 Binder resin solution (solid 4) obtained in Example-2
0%) 100 g and titanium dioxide 26 g in a sand mill
After kneading for 1 hour, 12.9 g of Desmodur Z4370, an isocyanate curing agent, was added, and paint preparation and coating film test were conducted in the same manner as in Formulation Example-1. The results are shown in Table 2.
It was shown to.

Reference Example-1 Chlorinated polypropylene Super Clone 832L (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 27 wt%, solid content 3)
0 wt%) 35 g and polyacrylic polyol Desmophen A-160 (manufactured by Sumitomo Bayer Urethane Co., Ltd., solid content 60%, hydroxyl group content 2.7% vs. solid) 35
g, Titanium dioxide 26g, Death module Z4370
A paint preparation and a coating film test were conducted in the same manner as in Formulation Example-1 at a blending ratio of 12.2 g. The results are shown in Table 2.

[0071]

[Table 2]

Test Method / Adhesiveness 100 grids that reach the substrate at 1 mm intervals were made on the coated surface, and cellophane adhesive tape was adhered on the grid to make 180
It was peeled off in the ° direction and judged by the extent to which the coating film remained.

Accelerated weather resistance A carbon arc type sunshine weather meter was used. The whiteness was measured by Hunter and the glossiness was measured by a 60 ° specular reflection gloss meter.

Hot water resistance The coated plate was immersed in hot water of 40 ° C. for 120 hours and 240 hours, and the state of the coating film was examined.

Gasoline resistance (rubbing 100 times) The absorbent cotton was impregnated with Nisseki Regular Gasoline, and the coated surface was rubbed 100 times to examine the state of the coating film. (Dip for 2 hours) A scratch (x) reaching the base material was put on the coated surface, and soaked in Nisseki regular gasoline for 2 hours, and the state of the coating film was examined.

Bending resistance The state of the coating film was examined by bending 180 ° with a 1 / 2φ inch mandrel.

Impact resistance: DuPont type impact tester, hammer core 1 / 2φ inch, load 5
Using 00g, drop it on the coated surface from a height of 50 cm,
The state of the coating film was examined.

As shown in Table 2, it is understood that the adhesion to polypropylene is equal to or higher than that of the conventional chlorinated resin, and the weather resistance is considerably improved as compared with the chlorinated resin. Further, the hot water resistance and the gasoline resistance are also greatly improved, and the bending resistance and the impact resistance are improved by using an acrylic acid ester as a main component in the radical polymerizable monomer. Comprehensive evaluation shows that the binder resin composition of the present invention has excellent performance as a paint.

Subsequently, regarding the performance when these binder resin compositions were applied to ink, Formulation Examples 3 and 4
Will be explained. Further, regarding the physical properties of the conventional chlorinated polyolefin resin and urethane resin, Reference Examples 2 and 3
showed that.

Formulation Example-3 The binder resin solution (solid 4) obtained in Example-1
0%) to adjust the ink and coating rod # 10 for untreated polypropylene film (hereinafter referred to as untreated PP), polyethylene terephthalate film (hereinafter PE).
(Referred to as T) and a nylon film (hereinafter referred to as NY), and dried at room temperature for 24 hours, and then subjected to a cellophane peel test and a heat seal strength test using a cellophane adhesive tape. The results are shown in Table 4. The formulation of the ink is shown in Table 3.

Formulation Example-4 The binder resin solution obtained in Example-2 (solid 4
The ink was adjusted to 0%), and the same test as the following formulation example-3 was performed. The results are shown in Table 4.

Reference Example-2 Chlorinated Polypropylene Super Clone 803MW (Sanyo Kokusaku Pulp Co., Ltd., chlorine content 29.5 wt%, solid content 20 wt%) and chlorinated ethylene vinyl acetate copolymer
The ink was adjusted with a mixture of Super Clon BX (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 18% by weight, solid content 20% by weight), and the same test as in Formulation Example-3 was performed below. The results are shown in Table 4.

Reference Example-3 Polyurethane Resin Ink was prepared with Sambrene IB-450 (manufactured by Sanyo Kasei Chemical Industry Co., Ltd., solid content 30 wt%), and the same test as in Formulation Example-3 was conducted. The results are shown in Table 4.
It was shown to.

As can be seen from Table 4, the examples using the binder resin of the present invention show excellent adhesion to any film of polypropylene (PP), polyethylene terephthalate (PET), etc. It is possible to prepare a general-purpose ink that combines the properties of chemical resin and polyurethane resin.

[0085]

[Table 3] ・ Titanium dioxide (made by Ishihara Sangyo Co., Ltd., rutile type R-8
20) ・ Carmine 6BN (Azo organic pigment manufactured by Toyo Ink Mfg. Co., Ltd.) ・ Ink kneading conditions: Kneading in a sand mill for 2 hours

[0086]

[Table 4]

Cellophane tape peeling test The cellophane adhesive tape was attached on the ink coated surface, and the peeled state of the coated surface when peeled off at once was judged.

Heat Seal Strength Test The ink coated surfaces were overlapped and heat sealed under a pressure bonding condition of 110 ° C.-1 kg / cm ² for 1 second, and after 24 hours, a 180 ° peel strength test was performed using Tensilon ( Tensile speed 50mm / min)

[0089]

As described in the above examples, the binder resin composition obtained by the present invention and the method for producing the same do not cause the deterioration of weather resistance found in chlorinated polyolefin-based binder resins, and the conventional non-chlorine compounds. It has little cross-linking and gelation found in polyolefin-based grafts and has adhesiveness to polyolefins, and can be used as films, sheets or molded products of various synthetic resins such as polyurethane-based resins, polyamide-based resins, acrylic-based resins, polyester-based resins, etc. On the other hand, it has become possible to provide a binder resin composition for paints, printing inks, or adhesives, which exhibits excellent physical properties.

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[Procedure amendment]

[Submission date] April 30, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

In order to improve these drawbacks, Japanese Patent Laid-Open No.
No. 71966, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin, and an acrylic resin having a hydroxyl group, as shown in JP-A-59-27968. A coating composition comprising a chlorinated polyolefin-modified hydroxy group-containing acrylic copolymer obtained by copolymerizing a monomer and the like with a chlorinated polyolefin and an isocyanate compound as essential components, and JP-A-62-9537.
Adhesive comprising a hydroxyl group-containing acryl-modified chlorinated polyolefin copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber and an isocyanate compound as main components, as seen in JP-A-2 Resin compositions and the like have been proposed. However, these chlorine-containing compositions are slightly inferior in ultraviolet resistance and heat resistance and have a problem in long-term weather resistance.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

A composition containing no chlorine is disclosed in Japanese Patent Laid-Open No.
JP-A-2-273083 proposes a method for forming a multilayer coating film comprising a resin composition obtained by copolymerizing a polyolefin graft-polymerized with maleic acid, a functional group monomer and a radically polymerizable unsaturated monomer, and a crosslinking agent. .. In addition, a method of introducing an unsaturated bond into polyolefin (Japanese Patent Application Laid-Open No. 1-123812, Japanese Patent Application Laid-Open No. 2-269109).
JP-A-1-1).
No. 31220), a method using a bifunctional organic peroxide (Japanese Patent Laid-Open No. 64-36614) and the like have been proposed, but these all improve the reactivity of the polyolefin and the radically polymerizable unsaturated monomer. It is a device for making it happen.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0080

[Correction method] Change

[Correction content]

Formulation Example-3 The binder resin solution (solid 4) obtained in Example-1
0%) to adjust the ink and coating rod # 10 for untreated polypropylene film (hereinafter referred to as untreated PP), polyethylene terephthalate film (hereinafter PE).
(Referred to as T) and a nylon film (hereinafter referred to as NY), and dried at room temperature for 24 hours, and then subjected to a cellophane peel test and a heat seal strength test using a cellophane adhesive tape. The results are shown in Table 4. The formulation of the ink is shown in Table 3 in parts by weight.

Claims (8)

[Claims] 1. Propylene, ethylene, and a carbon number of 4 to 20
Obtained by decomposing a polyolefin obtained by random copolymerization of α-olefin with organic peroxide and / or heat 20
~ 80% by weight, at least 50 mol% has 4 to 4 carbon atoms
A binder resin composition having a uniform transparency of a resin solution, which is obtained by adding 80 to 20% by weight of a radically polymerizable monomer which is an acrylic acid ester of 12 and performing graft polymerization. 2. The binder resin composition according to claim 1, which is obtained by dissolving a polyolefin in an organic solvent at a solid content concentration of 20 to 50% by weight. 3. A radical-polymerizable monomer having a concentration in the reaction solution of 1 after the organic peroxide is added to the polyolefin solution.
The vine-ider resin composition according to claim 1 or 2, which is obtained by gradually adding it in a range not exceeding 0.5 mol per liter. 4. The binder resin composition according to claim 1, which is obtained by carrying out the reaction at a temperature at which the half-life of the organic peroxide is 3 to 5 hours. 5. Propylene, ethylene, and a carbon number of 4 to 20
Polyolefins obtained by random copolymerization of α-olefins of above are degraded by organic peroxide and / or heat 20 to
80 to 20% by weight of radically polymerizable monomer
When added by weight% for graft polymerization, the following (a) and (b)
(c) (d) (a) Polyolefin in an organic solvent having a solid content concentration of 20 to
Dissolves in the range of 50% by weight, (b) within a range such that the concentration of the radical-polymerizable monomer in the reaction solution does not exceed 0.5 mol after addition of the organic peroxide to the polyolefin solution. Gradually added, (c) At least 50 mol% of the radical-polymerizable monomer is an acrylate ester having 4 to 12 carbon atoms, (d) Temperature at which half-life of organic peroxide is 3 to 5 hours 1), 2), 3)
A binder resin composition having good transparency of a resin solution obtained by combining two or all of them. 6. A binder resin composition in which 1 to 100 mol% of the acrylic acid ester according to claim 1 is cyclohexyl acrylate. 7. A method for producing the binder resin composition obtained by any one of claims 1 to 5. 8. A binder resin composition for paints and inks and adhesives, which comprises the resin obtained according to any one of claims 1 to 7.