JPS6310161B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a novel modified resin suitable as a resin for printing ink, and more specifically, a cyclopentadiene resin, a higher fatty acid ester, a hydroxyl group-containing modifier, a silicon compound, and optionally an α,β-unsaturated dicarboxylic acid. This invention relates to a method for producing a novel modified resin using an anhydride. In recent years, much research has been conducted to improve lithographic printing technology, and one example of this is the development of a dry lithographic printing method that uses a thin film made of a non-adhesive material such as silicone rubber for non-image areas. This method eliminates the need for dampening water, so it eliminates the problems that often occur with dampening water in conventional lithographic printing methods (for example, emulsification of printing ink, loss of gloss due to water loss, set-off, ghosting, etc.). (e.g., the occurrence of blemishes, etc.), and excellent printing effects can be obtained. However, if this method is used to print at high speeds for a long period of time using regular ink, the temperature on the printing plate will rise, causing the ink to adhere to non-image areas and easily causing plate staining. As a means to solve this problem, methods have been proposed in which various ink materials are modified with silicon compounds. For example, silicon-modified alkyd resin (Japanese Patent Publication No. 51-10124, Japanese Patent Publication No. 51-22405), silicon-modified vegetable oil (Japanese Patent Publication No. 52-10041, Japanese Patent Publication No. 52-10042),
Silicone-modified oil-soluble phenolic resin
60706, No. 52-62506), but these methods are not sufficiently effective in improving plate staining, and it is desired to develop ink materials that cause even less plate staining. Ta. Therefore, an object of the present invention is to provide a method for producing a modified resin suitable as a vehicle for dry planographic printing ink that causes less plate staining at high temperatures.
The object of the present invention is to produce a reaction product of (a) a cyclopentadiene resin and (b) a higher fatty acid ester having a conjugated double bond, or both components (a) and (b) and (c)
A hydroxyl group-containing resin () obtained by reacting the reaction product (I) of an α,β-unsaturated dicarboxylic acid anhydride with (d) a hydroxyl group-containing modifier (e) a hydroxyl group or an alkoxy group bonded to a silicon atom This is achieved by reacting a silicon compound containing . The reaction product (I) used in the present invention is usually
(a) Cyclopentadiene resin 98-35% by weight, preferably 95-50% by weight, (b) Higher fatty acid ester having a conjugated double bond 2-65% by weight, preferably 5-5% by weight
(c) unsaturated dicarboxylic acid anhydride 0-30% by weight, preferably 0.3-15% by weight of the reaction product. At this time, if the amount of component (b) is small, the wettability with the pigment will be poor, whereas if it is large, gelation will easily occur during the reaction. In addition, the presence of component (c) further improves pigment wettability and suppresses gel by-products, but if too much is present, the hue deteriorates and the plate is likely to smear when used as an ink. Become. (a) used in the synthesis of reaction product (I)
The component is prepared by a conventional method using a cyclopentadiene monomer such as cyclopentadiene, methylcyclopentadiene, dimer, trimer, codimer, etc., or a cyclopentadiene monomer in a subordinate position. It is obtained by thermally polymerizing a mixture of this and a comonomer that can be copolymerized, and has a softening point of 80~
Those with a Gardner chromaticity of 13 or less at 200℃, especially 100 to 170℃, are prized. Specific examples of comonomers used include monoolefins such as ethylene, propylene, butene, and styrene, 1,3-butadiene, isoprene,
Examples include conjugated dienes such as 1.3-pentadiene, and polar vinyl monomers such as vinyl acetate, acrylic esters, methacrylic esters, acrylonitrile, and allyl alcohol. Among these, homopolymers of cyclopentadiene monomers or copolymers of cyclopentadiene monomers with hydrocarbon comonomers such as moreolefin and conjugated dienes are preferred. On the other hand, component (b) consists of a monocarboxylic acid having 12 or more carbon atoms and a conjugated double bond in the molecular chain, such as eleostearic acid and parinaric acid, methanol, ethanol, butanol, octanol, ethylene glycol, glycerin, Such as pentaerythritol, trimethylolpropane, etc.1
These are esters with alcohols or polyhydric alcohols, and among them, triester of glycerin is preferred.
These glycerin triesters are contained in natural drying oils such as tung oil, dehydrated castor oil, oiticica oil, and eno oil, and in the present invention, these natural drying oils are used as higher fatty acid esters. Specific examples of component (c) include maleic anhydride, citraconic anhydride, itaconic anhydride, and alkyl substituted products thereof. will be awarded. The reaction product (I) may be a product obtained by reacting these three components in any order, and is not particularly limited by the order of the reactions, but may be a reaction product that is polymerized while preventing gelation. In order to obtain the product, it is preferable to form an adduct of components (a) and (c) and an adduct of components (b) and (c) in advance and then react them. (c) without adding any component (a)
When reacting the component with the component (b), sufficient care must be taken to control the reaction since gelation of the component (b) tends to proceed. The reaction of each component is usually carried out at 190-300℃ under an atmosphere of inert gas such as nitrogen or argon.
It will be carried out for 30 minutes to 8 hours, and at this time, (a)
When forming an adduct between a component and a component (c) or an adduct between a component (b) and a component (c) in advance, the component (a) or the component (b) and the component (c) are prepared by a conventional method. According to e.g. 150
A method of preparing in advance by reacting at ~250℃ for about 10 minutes to 5 hours, and reacting components (a), (b), and (c) simultaneously to form each adduct in the system. You may follow any method. In this case, the amount of component (c) used is the same as that of component (a).
(b) 100% of each component in order to increase the reactivity with the component.
It is preferably 0.1 part by weight or more, and usually 0.2 to 30 parts by weight. In particular, when modifying into an ink resin, it is appropriate to use 0.3 to 15 parts by weight per 100 parts by weight of each of component (a) and component (b). This reaction is usually carried out in the absence of a diluent, but diluents can be used if desired, such as common hydrocarbon solvents such as benzene, toluene, xylene, tetralin, mineral oil, etc., as well as linseed Examples include natural oils that are inert to the reaction, such as oil and soybean oil. Also, if desired, titanium,
Compounds of metals such as zirconium, tin, lead, etc. can also be used as catalysts. In the present invention, the hydroxyl group-containing resin (2) is obtained by reacting the reaction product (I) thus obtained with the hydroxyl group-containing modifier (d).
The hydroxyl group-containing modifier to be subjected to the reaction may be any one that can introduce a hydroxyl group into the reaction product (I) through reaction with the reaction product (I), such as an acid anhydride group. Polyhydric alcohols and alkanolamines are examples of modifiers that utilize a reaction with unsaturated bonds, and unsaturated acid esters containing hydroxyl groups are examples of modifiers that utilize an addition reaction to unsaturated bonds. Specific examples of such modifiers include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, solpitol,
Low molecular weight polyhydric alcohols such as diglycerol, bis(hydroxylmethyl)benzene, etc.; Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, etc.; dicyclopentadiene-allyl alcohol copolymer resin, styrene-allyl alcohol copolymer resin Resinous polyhydric alcohols such as castor oil, polyethylene glycol, polypropylene glycol, etc.; Hydroxyl group-containing unsaturated acid esters such as hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, etc.; N-methylol Examples include hydroxyl group-containing unsaturated acid amides such as acrylamide and N-methylolmethacrylamide. The reaction between reaction product (I) and component (d) is usually 80~
It is carried out at 280°C for 10 minutes to 5 hours. The amount of the hydroxyl group-containing modifier used is appropriately selected, but is usually in a range such that the hydroxyl value of the hydroxyl group-containing resin () to be produced is 1 to 120, preferably 3 to 100. In the present invention, a modified resin is obtained by reacting the thus obtained hydroxyl group-containing resin (2) with (e) a silicon compound containing a hydroxyl group or an alkoxy group bonded to a silicon atom. The silicon compound to be subjected to the reaction contains at least one silicon compound in the molecule.
Any material having hydroxyl or alkoxy groups may be used, specifically vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. Alkoxysilane compounds; hydroxyl group-containing organopolysiloxanes such as hydroxyl group-containing polydimethylsiloxanes, hydroxyl group-containing dimethylsiloxane/diphenylsiloxane copolymers; methoxy group-containing polydimethylsiloxanes, methoxy group-containing dimethylsiloxane/diphenylsiloxane copolymers, etc. Examples include alkoxy group-containing organopolysiloxanes such as the following. The reaction between the hydroxyl group-containing resin () and the silicon compound (e) is usually carried out at a temperature of 50 to 250°C, preferably 100 to 200°C for 30°C.
The silicon compound is introduced into the resin by a dehydration reaction between the hydroxyl group in the resin and the hydroxyl group in the silicon compound or a dealcoholization reaction with an alkoxy group. The amount of (e) silicon compound used can vary over a wide range, but usually ranges from 1 to 80 parts by weight of hydroxyl-containing resin ().
Part by weight, preferably 5 to 60 parts by weight, and the amount of hydroxyl or alkoxy group in the silicon compound is 0.3 to 4 per equivalent of hydroxyl group in the hydroxyl group-containing resin ().
It is appropriate that the amount is equivalent, more preferably 0.5 to 3 equivalents. In this way, by introducing the silicon compound (e) into the hydroxyl group-containing resin (2), a modified resin can be obtained that can be used to prepare a printing ink for dry planography with improved plate staining at high temperatures. Among them, (a) adducts of cyclopentadiene resins and (c) α.β-unsaturated dicarboxylic acid anhydrides, and (b) higher fatty acid esters (c) additions with α.β-unsaturated dicarboxylic acid anhydrides. The reaction product obtained by reacting both adducts of a compound has superior performance as an ink resin compared to conventional cyclopentadiene resins (Japanese Patent Application Laid-Open No. 125494-1982).
(I).
When used as a modified resin, a particularly good modified resin can be obtained. The modified resin of the present invention thus obtained usually has a softening point of 40 to 180°C, and can be used in paints, adhesives,
In addition to being used in fields where cyclopentadiene resins are commonly used, such as varnish, it is particularly suitable as an ink resin, and is particularly useful as a vehicle for dry lithographic printing inks. The present invention will be explained in more detail with reference to Examples below. Note that parts and percentages in Examples are based on weight unless otherwise specified. Example 1 Cyclopentadiene in the presence of xylene at 260
Cyclopentadiene resin with a softening point of 135°C and a Gardner chromaticity of 4 obtained by thermal polymerization at ℃ for 4 hours.
After heating and melting 100 parts and 50 parts of tung oil at 170℃,
5 parts of maleic anhydride was added and reacted at 180°C for 1 hour, and 1 part of zirconium octenoate was added, the temperature was raised to 240°C, and reaction was carried out for 5 hours. To 100 parts of the reaction product obtained in this way, 6.8 parts of trimethylolpropane was added and the reaction was carried out at 160°C for 1 hour, resulting in a softening point of 128°C, acid value of 18, and hydroxyl value.
35 hydroxyl group-containing resins were obtained. Next, a predetermined amount of hydroxyl group-containing polydimethylsiloxane (silicone oil RFL manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group content 3.1%) is applied to 100 parts of this hydroxyl group-containing resin.
was charged and a condensation reaction was carried out at 160°C for 3 hours to obtain a modified resin. The softening point and Gardner chromaticity of the obtained modified resin were measured, and then 40 parts of the modified resin was dissolved in 60 parts of petroleum solvent (Nippon Oil Co., Ltd., No. 5 Solvent), and the viscosity (Gardner display) was measured. It was measured. In addition, 100 parts of modified resin and 42.8 parts of petroleum solvent were heated to 180°C.
Make a varnish by heating and stirring for 20 minutes.
After adding 20 parts of phthalocyanine blue (manufactured by Dainippon Ink Co., Ltd., TGR) to 100 parts and kneading with three rolls, an ink with an inkometer value of 11.0 (400 rpm) was prepared by further adding a small amount of petroleum solvent. The ink thus obtained is Heidel.
Transferred onto a silicone dry lithography plate (manufactured by Toray Industries, Inc.) using a KORD monochromatic machine, observed the adhesion of ink to non-image areas at plate surface temperatures of 20°C and 40°C, and transferred onto coated paper using the same method. Color and set were measured. For comparison, we synthesized a silicone-modified alkyd resin that has been used in the past and evaluated it in the same manner. The results are shown in Table 1.

[Table] From these results, the ink using the modified resin of the present invention shows less adhesion to the non-printing areas of silicone dry lithographic plates even at 20°C or even 40°C, and also has extremely excellent performance in terms of setting. It can be seen that this shows that On the other hand, the silicone-modified alkyd resins that have been used in the past are inferior in terms of setting and have some difficulty in adhesion at high temperatures. Example 2 An experiment was conducted in the same manner as experiment number (1-3) of Example 1 except that a hydroxyl group-containing silicone varnish (Silicon Varnish KR216 manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group content 5.5%) was used as the silicon compound, and softening was performed. point
A modified resin having a Gardner color number of 15 at 132°C and a solution viscosity of T to U was obtained. An ink was prepared using this modified resin in the same manner as in Example 1, and its performance was evaluated. As a result, the ink adhesion to the non-image areas of a silicone dry lithography plate was 20.
℃ and 40℃, and the setting time was 10 minutes. Example 3 A methoxy group-containing silicone varnish (manufactured by Shin-Etsu Chemical Co., Ltd., silicone varnish KR218,
An experiment was carried out in the same manner as in Experiment No. (1-3) of Example 1, except that methoxy group content 15%) was used, and a modified resin with a softening point of 120°C, a Gardner color number of 15, and a solution viscosity of R was obtained. . An ink was prepared using this modified resin in the same manner as in Example 1, and its performance was evaluated.
It was not observed at either temperatures of 40°C or 40°C, and it took 8 minutes to set.

Claims (1)

[Scope of Claims] 1. A reaction product of (a) a cyclopentadiene resin and (b) a higher fatty acid ester having a conjugated double bond, or both components (a) and (b) above, and (c) α, β- A hydroxyl group-containing resin (2) obtained by reacting the reaction product (I) of an unsaturated dicarboxylic acid anhydride with (d) a hydroxyl group-containing modifier, and (e) silicon containing a hydroxyl group or an alkoxy group bonded to a silicon atom. A method for producing a novel modified resin () characterized by reacting compounds. 2. The method according to claim 1, wherein the modified resin has a softening point of 40 to 180°C.