JPH0610253B2 - Vehicle resin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin for vehicles, which is composed of a saturated polyester having a specific molecular structure, particularly for printing inks, and a resin for vehicles used for various purposes.

Conventional technologyScreen printing is advantageous in that plate making and printing are simple, thick printing can be performed, it is not affected by the shape and surface condition of the material to be printed, and it is suitable for high-mix low-volume printing. Yes, and has made remarkable progress in recent years.

In addition to paper, plastics films are also widely used as materials to be printed by screen printing.
Metal, rubber, leather, glass, ceramics and wood are also used.

Conventionally, nitrocellulose has been used as a resin for vehicle of screen-printing ink, which is of natural drying type or hot air drying type.
Ethyl cellulose, hydroxyethyl cellulose, maleic acid resin, rosin ester, chlorinated rubber, deoxidized rubber, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, urethane resin, polyamide resin, alkyd resin, linseed oil varnish, modified phenolic resin Various things are known.

Problems to be Solved by the Invention As described above, various kinds of resins for vehicles for screen printing inks are known, but recently, a plastic film having a smooth surface and hydrophobicity as an object to be printed. Since it tends to be used in large quantities, it is necessary to obtain sufficient adhesion not only to paper but also to plastic films. Also, applications that require flexibility, solvent resistance (especially alcohol resistance) ) Is increasing in number of applications, and it is desired to develop a resin for vehicles that can handle such applications.

However, vehicle resins with good alcohol resistance generally have high glass transition points, which limits their use in applications where the resin becomes hard and requires flexibility. On the other hand, vehicle resins with flexibility are limited. Generally, since the glass transition point is low, the alcohol resistance tends to be poor, and as a result, a vehicle resin having both alcohol resistance and flexibility cannot be easily obtained.

Therefore, conventionally, a vehicle resin suitable for the application requiring alcohol resistance, or a vehicle resin suitable for the application requiring flexibility is selected.
It has been customary to sacrifice both alcohol resistance and flexibility a little, and to select a vehicle resin having a compromised property of both.

However, recently, there are many applications in which alcohol resistance and flexibility are required at the same time, and at that time, the advent of an ink having adhesion to a plastic film and other printability is desired. There is a long-awaited development of a vehicle resin for inks that meets various demands.

Further, the resin having such properties is useful not only as a vehicle resin for inks but also as a vehicle resin for applications such as paints, coating agents and adhesives, and also has the above properties in these fields. The development of vehicle resins is highly anticipated.

In view of such a situation, the present invention has been achieved as a result of earnest studies to find a vehicle resin having alcohol resistance, flexibility, and adhesion to a plastic film.

Means for Solving the Problems In the vehicle resin of the present invention, 1 to 20 mol% of the polyhydric alcohol component of a saturated polyester composed of a saturated polybasic acid component and a polyhydric alcohol component is trivalent. A partially esterified product of the above polyhydric alcohol with a rosin-based compound, which is composed of a saturated polyester having at least two hydroxyl groups remaining in its molecule and having a molecular weight in the range of 8,000 to 50,000. To do.

The present invention will be described in detail below.

The vehicle resin of the present invention is a saturated polyester, that is, a saturated polybasic acid is used as the polybasic acid component and is condensed with a polyhydric alcohol component. 1 to 20 of alcohol components
It is necessary that the mol% is a partial esterified product of a rosin compound of a polyhydric alcohol having a valence of 3 or more and at least two hydroxyl groups remain in the molecule.

Here, as the rosin compound, natural rosin (main component abietic acid), rosin constituent components (abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, d-pimaric acid, iso-d-pimaric acid, Dehydroabietic acid, etc.), isomerized rosin, dimerized rosin, polymerized rosin, or hydrogenated products thereof. Among these, hydrogenated products that are not easily colored during storage are particularly preferable.

Examples of the polyhydric alcohol include polyhydric alcohols having at least three hydroxyl groups in the molecule. Examples of such polyhydric alcohols include glycerin, trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, diglycerin and sorbitol.

Since the partial esterified product of the polyhydric alcohol of the rosin-based compound is used as a part of the polyhydric alcohol component forming the saturated polyester, the ester gum (resin of rosin of the type used as a resin for vehicle of conventional ink is used. Glycerin or pentaerythritol ester of rosin, not all of the hydroxyl groups of glycerin or pentaerythritol are esterified, but it is required to be a partial esterified product in which at least two hydroxyl groups remain in the molecule. .

Incidentally, conventionally known saturated rosin polyester,
For example, when natural rosin is used as the condensation component, the reactivity is not good as it is, and it is difficult to increase the molecular weight as in the present invention by an ordinary polyester production method. That is, as a means for increasing the molecular weight, it is conceivable to lengthen the reaction time or raise the reaction temperature, but in the case of the former, it takes an extremely long time for the reaction, so that it lacks industrial properties, while in the case of the latter, In order to achieve this, the reaction temperature must be around 300 ° C. or higher, but when the temperature is raised in this way, the resin becomes colored.
After all, the upper limit of the molecular weight of the rosin-modified saturated polyester obtained by a practically employable production method is about 5,000, and therefore the physical properties of the coating film are extremely insufficient.

The proportion of the above partial esterified product in the polyhydric alcohol component constituting the saturated polyester is selected from the range of 1 to 20 mol%, and when the proportion is less than 1 mol%, alcohol resistance, flexibility, and plastic film Adhesiveness cannot be obtained at the same time, and on the other hand, when the ratio exceeds 20 mol%, the degree of condensation of the saturated polyester becomes difficult to increase,
The strength of the ink film or coating film becomes insufficient. A particularly preferred range is 2 to 12 mol%.

The saturated polybasic acid component constituting the saturated polyester includes terephthalic acid, isophthalic acid, phthalic acid, 2,5-norbornanedicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, diphenic acid, 4,4 '-Oxybenzoic acid, diglycolic acid, thiodipropionic acid, 4,4'-sulfonyldibenzoic acid, 2,5-naphthalenedicarboxylic acid, oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipine Acid, dodecanedicarboxylic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, sebacic acid, 1,3-
Examples thereof include cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.

As the polyhydric alcohol component other than the partial esterified product constituting the saturated polyester, ethylene glycol,
Propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 2-ethyl -1,3-hexanediol, 2,
Examples include glycols such as 2,4-trimethyl-1,3-pentanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol. In addition, trimethylolethane,
A small amount of trihydric or higher alcohol such as trimethylolpropane, glycerin and pentaerythritol can be used together.

And, this saturated polyester, for the purpose of the present invention,
The molecular weight is required to be in the range of 8,000 to 50,000. If the molecular weight is less than 8,000, the film strength is low, so the printing ink properties, coating suitability, etc. are poor.On the other hand, if the molecular weight is more than 50,000, the viscosity when dissolved in a solvent is too high and the handling is poor. Like

The condensation reaction between the polybasic acid component and the polyhydric alcohol component is usually carried out by performing a first-stage reaction under an inert gas atmosphere at a temperature of about 150 to 260 ° C., and then performing a second-stage reaction at about 220 to 280 ° C. under high vacuum. Good to do.

The saturated polyester thus obtained is useful as a vehicle resin for printing inks (particularly for screen printing inks), a vehicle resin for paints, coating agents and adhesives.

Printing inks consist of colorants, vehicles and additives.

Among these, as the color material, pigments such as inorganic pigments (titanium oxide, carbon black, bronze powder, etc.) or organic pigments (azo pigment, phthalocyanine pigment, dyeing lake pigment, etc.), acidic dyes, basic dyes, oil-soluble dyes, Dyes such as disperse dyes are used.

The vehicle is composed of oil (vegetable oil, processed oil, mineral oil, etc.), the above-mentioned vehicle resin, solvent (hydrocarbon, ester, ketone, glycol, cellosolve, etc.), plasticizer, etc., and if necessary, modified cellulose, isocyanates. , Urethane resin, etc. can be used together.

The additives include waxes, drying agents (metal soap, etc.), dispersing agents, wetting agents, emulsifying agents, gelling agents, stabilizers, defoaming agents and the like.

The paint, coating agent, and adhesive have the same structure, but the use of colorants and additives may be omitted, and the blending of oil and plasticizer in the vehicle may be omitted.

Working The vehicle resin of the present invention forms a vehicle with oil, solvent, plasticizer and the like. Then, by mixing this vehicle with colorants and additives to prepare inks, paints, coating agents, adhesives, etc., and applying it to the target object, the partial ester of the polyhydric alcohol of the rosin compound introduced into the saturated polyester. Alcohol resistance, flexibility, and adhesion to plastics film can be obtained by the compound, and the molecular weight of saturated polyester is set in the range of 8,000 to 50,000, so the strength of the ink film, coating film and film after drying is maintained. Be drunk

EXAMPLES Next, the present invention will be further described with reference to Examples. Hereinafter, "part" and "%" are expressed on a weight basis.

Example 1 A four-necked flask equipped with a thermometer, a stirrer, and a packed column was charged with 0.4 mol of terephthalic acid, 0.4 mol of isophthalic acid, 0.2 mol of sebacic acid, and hydrogenated rosin monoester of trimethylolpropane 0.1 in a nitrogen stream. 1 mol with ethylene glycol 0.7 mol, neopentyl glycol 0.7 mol and dibutyltin oxide 0.1% (based on the total system)
Perform esterification reaction at 40-240 ℃, then add 0.1% antimony trioxide (based on the whole system) under reduced pressure of 1 Torr 2
The condensation was carried out at 20-260 ° C.

As a result of measurement by NMR, it was confirmed that the polyhydric alcohol component had a composition ratio of 9.8 mol% of partial esterified product, 44.4 mol% of ethylene glycol, and 45.8 mol% of neopentyl glycol.

The acid value of the obtained saturated polyester was 0.2 KOHmg / g, the melt viscosity was 2000 ps / 190 ° C, and the molecular weight was 16,000.

This saturated polyester was dissolved in cellosolve acetate to obtain a 40% concentration solution, and a dry thickness was applied on an untreated polyethylene terephthalate film using a doctor knife.
It was applied so as to have a thickness of 20μ, and dried by a hot air dryer at 80 ° C for 1 minute to form a film.

This film was subjected to a methanol rubbing test, and its flexibility and adhesion were examined.

The results are shown in Table 1.

Comparative Example 1 Acid value of 0.2 KOHmg / same as in Example 1 except that the charge of hydrogenated rosin monoester of trimethylolpropane was omitted and the charge amount of ethylene glycol was 0.8 mol.
g, a melt viscosity of 2,000 ps / 190 ° C., and a saturated polyester having a molecular weight of 18,000 were obtained, and the same experiment as in Example 1 was performed. The results are also shown in Table 1.

Example 2 0.4 mol of terephthalic acid, 0.3 mol of phthalic anhydride, 0.3 mol of adipic acid, 0.05 mol of rosin monoester of glycerin, 0.5 mol of ethylene glycol, 0.2 mol% of diethylene glycol and 0.75 mol of neopentyl glycol were used, and the same as in Example 1. And the condensation reaction was carried out.

The acid value of the obtained saturated polyester was 0.2 KOHmg / g, the melt viscosity was 1,300 ps / 190 ° C, and the molecular weight was 16,000.

As a result of measurement by NMR, the polyhydric alcohol component was a partial esterified product 4.7 mol%, ethylene glycol 31.7%,
It was confirmed that the composition ratio was 14.4 mol% of diethylene glycol and 49.2 mol% of neopentyl glycol.

Dissolve this saturated polyester in toluene to make a 40% solution, and apply it to a soft vinyl chloride film using a doctor knife to a dry thickness of 10μ by the doctor knives method, and at 20 ° C, 65% RH. It was naturally dried for 24 hours to form a film.

This film was subjected to a methanol rubbing test and examined for flexibility and weldability.

The results are shown in Table 2.

Comparative Example 2 The acid value was 0.2 KOHmg / g and the melt viscosity was 1,300 ps / 1 in the same manner as in Example 2 except that the rosin monoester of glycerin was omitted and the amount of ethylene glycol was changed to 0.55 mol.
Saturated polyester having a molecular weight of 17,000 and a temperature of 90 ° C. was obtained, and the same experiment as in Example 2 was performed. The results are also shown in Table 2.

Comparative Example 3 Terephthalic acid 0.4 mol, phthalic anhydride 0.3 mol, adipic acid 0.2 mol, natural rosin 0.1 mol, ethylene glycol 0.
A condensation reaction was carried out according to Example 1 using 6 mol, 0.2 mol% of diethylene glycol and 0.7 mol of neopentyl glycol to give an acid value of 14 KOHmg / g, a melt viscosity of 300 ps / 150 ° C and a molecular weight.
4,000 polyesters were obtained, and the same experiment as in Example 2 was conducted below. The results are also shown in Table 2.

It should be noted that this preparation composition with a higher molecular weight (target
To produce 10,000), condensation was carried out at a temperature of 300 ° C., but the reaction product was colored yellow within a few hours after the start of the reaction and could not be put to practical use.

Example 3 A screen-printing ink was prepared according to the following formulation, and printing was performed on the surface of a polyvinyl chloride sheet. It passed the methanol rubbing test 100 times, and the printed pattern did not fall off even when the sheet was bent. It was

Phthalocyanine blue 3 parts Titanium oxide 27 parts Saturated polyester obtained in Example 1 22 parts Cyclohexanone 10 parts Aromatic hydrocarbon solvent 34 parts Isophorone 3 parts Dioctyl phthalate 1 part Example 4 A clear paint was prepared according to the following formulation, and aluminum. The board was coated, but the solvent resistance (alcohol resistance) was 100 after 100 rubbing tests, and the cross-cut test showed good adhesion of 100/100.

Saturated polyester obtained in Example 2 30 parts Toluene 35 parts Methyl ethyl ketone 35 parts Effect of the invention The vehicle resin of the present invention has excellent solvent resistance (particularly alcohol resistance), flexibility, and plastic film adhesion. Since we also have this resin as a vehicle resin, we prepare printing inks, paints, coating agents, adhesives, etc. can get.

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Claims (3)

[Claims] 1. A 1 to 20 mol% of a polyhydric alcohol component of a saturated polyester composed of a saturated polybasic acid component and a polyhydric alcohol component is a part of a trihydric or higher polyhydric alcohol derived from a rosin compound. A vehicle resin comprising an esterified product having at least two hydroxyl groups remaining in its molecule, and a saturated polyester having a molecular weight in the range of 8,000 to 50,000. 2. The vehicle resin according to claim 1, which is for printing ink. 3. The vehicle resin according to claim 1, which is used for paints, coating agents or adhesives.