JPS5959770A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. excellent in adhesion and bonding strength, free from tack, well suited for laminating, etc., by incorporating isocyanate compds. and chlorinated rubber with polyester resins having particular properties. CONSTITUTION:One mol of an acid component yielded by mixing 20-80mol% isophthalic acid with other acid components (e.g., terephthalic acid, succinic acid) is reacted with about 1-15mol of a polyol component (e.g., ethylene glycol, glycerin) in the presence of catalysts to prepare a polyester resin having isophthalic acid of 20-80mol% in the acid component, a hydroxyl value of 12- 18KOHmg/g, and a number = average MW of 6,000-10,000. Then, 10-20wt% isocyanate compd. (e.g., 2,4-tolylene diisocyanate) and 25-50wt% chlorinated rubber are incorporated with said resin to yield the intended adhesive compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition mainly composed of a polyester resin that has excellent adhesion and adhesive strength and does not cause tack.

Adhesives made of polyester resin and isocyanate compounds have been used for paper and other materials due to their excellent adhesion properties.
It is used in a variety of fields including wood, and the adhesive can be used not only for substrates with such polar groups, but also for non-polar substrates such as polyester film, polypropylene fissile, and polypropylene synthetic paper. , lamination of vinyl chloride meat, etc.) and processing adhesives ↑11
In short, it is growing. However, adhesives for such lamination processing are required not only to have good adhesive performance but also to have low tackiness, and polyester resin/isocyanate compound adhesives do not necessarily satisfy such performance. Specifically, one method of laminating using polyester resin as an adhesive is to apply the adhesive to the base material, overlap the objects to be adhered, and press them. Since the coated substrates are usually stored in a stacked manner until they are press-bonded, it is necessary to prevent the substrates from blocking each other during storage. Therefore, until now, operations such as adding various anti-blocking agents or inserting release paper have been unavoidable. In the latter case, there is a problem that the operating efficiency cannot be avoided.

Therefore, the inventors of the present invention aimed to develop a polyester resin adhesive that does not have tack while maintaining excellent adhesion and adhesive strength.
m'; I/9, an adhesive composition consisting of a polyester resin with a number average molecular % of 6000 to +[]ODD, an isocyanate compound of 10 to 20% by weight based on the resin, and 25 to 50 weight% of chlorinated rubber. It was discovered that the above-mentioned problems were satisfied, and the failure 1 was completed.

It is essential that the acid component of the polyester resin used in "Kidatsu" is 20 to 80 mol%, more preferably 50 to 60 mol%, of isophthalic acid. If the isophthalic acid content is less than 20 mol%, the resin will not dissolve in general-purpose solvents such as ethyl acetate or toluene, and if it is used in excess of 80 mol%, the glass transition point will become high, which is undesirable for use.

Other acid components are not particularly limited and include carboxylic acids commonly used in the production of polyester resins, such as terephthalic acid, orthophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, and 1,5-naphthalic acid. acid, p-oxybenzoic acid, and their strong alkyl partial esters, acid anhydrides, and the like.

The polyhydric alcohol components constituting the polyester resin include ethylene glycol, neopentyl glycol, fluoropylene gellicol, +, 57" lovandiol, 1,4
-butanediol, 1,5-pencunediol, 1,6
- Dihydric alcohols such as hekitune diol, diethylene glycol, dipropylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A1 and hydrogenated bisphenol A are the most common, but trimethylolethane, trimethylolpropane, chrycerin, Polyhydric alcohols with a valence of 6 or higher, such as pentaerythritol, can also be used as appropriate as long as gelation does not occur.

In addition to the 1f1 acid component and the polyhydric alcohol component, a small amount of 111-1 compound, such as a vinyl compound, which can react with these components, can also be used.

For producing the polyester resin of the present invention, any commonly used method may be employed. Typically acid component 1
A stirrer with the polyhydric alcohol component at a ratio of 1.0 to 1.5 moles per mole at once or in order of Vi together with the esterification catalyst;
The mixture is charged into a reaction vessel equipped with a full condenser, partial condenser, and torque meter, and esterification is carried out at a temperature of 150 to 250°C. As the esterification catalyst, dibutyl tin oxide, zinc acetate, etc. are used. Thereafter, the pressure was reduced to 0.5 to 1.0 gHg in the presence of a stabilizer and a polycondensation catalyst, and the temperature was 240 to 28%.
The double bond reaction is carried out at 0°C. Phosphoric acid, triethyl phosphoric acid is used as a stabilizer, and germanium oxide is used as a heavy powder mixing medium.
Examples include antimony trioxide and tetrapudyl titanate.

In this way, the polyester material that can be stopped has a hydroxyl value of 12 to 18 KOHw, making it more flexible.14
~ + 6KOHmVli', number running average molecule is 6000-
Must be 10000. Hydroxyl value is 12KOH
When sowing from I
If it is higher than B, the crosslinking density will be high, the pot life will be shortened, and the adhesive strength will be low, which is not preferable. In addition, the number average molecular weight is 6000.1: There is a tendency for the cohesive force of the polymer molecules of the polyester resin itself to decrease and the adhesive strength to decrease.
If it is higher than +oooo, the adhesion will be poor, which is not suitable.

The isocyanate compound added to the polyester resin is used in an amount of 10 to 20% by weight based on the polyester resin. If the amount is less than 10 times, the adhesive strength will deteriorate, and if it is more than 20'ffl%, gelation will occur, making it unsuitable for use. Incyanate compounds include 2,4-tolylene diisocyanate, 2.6-1-lylene diisocyanate, 2. l and 2
．． 6-Tolylene diisocyanate mixture, 4.4'-
Diphenylmethane diisocyanate, meta-phenylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexylmethane diisocyanate, lysine diisocyanate ester, 1.4
Examples include -cyclohexylene diisocyanate, 4,4-dicyclohexylphthane diisocyanate-1-1, and 1,5-naphthalene diisocyanate.

(!uL, the incyanate compound of Unexploded 1131-1 is not limited to these.

In case of failure 1, it is essential to further blend chlorinated rubber. The chlorinated rubber is generally a compound having the following structure.

In the formula, n is a natural number. The chlorine content in the chlorinated rubber is not particularly limited, but 50 to 70% by weight is usually preferred because it is easily available as a commercially available product. The optimal blending amount is 25 to 50% by weight based on the polyester resin. If it is sown at 25% by weight, C tack will occur, and if it is more than 50% by weight, there will be a significant decrease in adhesive strength, which is unwise. By blending such a specific amount of chlorinated rubber, the total height of contact force KNl can be increased for the first time.
This makes it possible to prevent tack while also maintaining the tuck.

The adhesive composition of the present invention is typically prepared using a solvent such as toluene,
It is used by appropriately dissolving it in a liquid or a mixture of benzene, xylene, acetate, ethyl acetate, butyl acetate, dioxane, tetrahydroalan, cyclohexanone, methyl ethyl ketone, phenol, and the like.

The composition exhibits excellent adhesion and adhesive properties as an adhesive when laminating polypropylene synthetic paper. Moreover, it is a dud F! According to 4, it is not limited to the synthetic paper, but also polypropylene film, for which good effects could not be obtained with conventional adhesives, as well as polyvinyl chloride, poly(meth)acrylic ester, polycarbonate, polyx stool. It is also useful as an adhesive for combinations of the same or different types of films, sheets, and plate-shaped moldings made of nylon, polyethylene, polyacetal, polystyrene, etc., and the length Vc is also excellent for adhesion to wood, paper, etc. It has an effect.

EXAMPLES The present invention will be specifically explained below with reference to Examples.

Production example of polyester resin (a) 0059 mol of isophthalic acid, 0.59 mol of terental acid, 46 mol of sepacin eo, ethylene glycol 1, Q
1.45 mol of neopentyl glycol and 6XlO' mol of digiltin oxide were charged into a 1/2 volume flask in the presence of a catalyst. "React at ℃~200℃,
Next, the reaction was carried out at 250'C under reduced pressure of 1 torr or less, and the molecular weight was 7500. A polyester resin having a hydroxyl value of 15 KOHwf and a glass transition point of 20° C. was obtained.

Cleavage-Bafujage 1-Fatness p1 Rikutsu L-Isophthalic acid 0
．． 77 mol, terephthalic acid 0.83 mol, adipic acid 0
．． 28 mol, ethylene glycol 2.64 mol, and triethylene glycol 0.19 mol. Hydroxyl value +
A polyester resin containing 17 g/7 of 5 KOH and a glass transition point of 23° C. was obtained.

Production example of polyester resin (c) Isophthalic acid 0.91 mol, terephthalic acid 0.81 mol, ethylene glycol +, + 2 mol, neopentyl glycol 0.77 mol, diethylene glycol 0.68 mol
The reaction was carried out in the same way as in the dlO description using moles,
Molecular weight 10000. Hydroxyl value 14 KOHm9/'! .

A polyester resin having a glass transition point of 25°C was obtained.

For comparison, the composition is the same as resin (a), but the resin (gradient is molecular weight 20,000, hydroxyl value 6, KOH place V1, glass transition point 20°C1 material) Fat (e) has a molecule of 1f28000, hydroxyl value 4 KOHwf, glass transition point 20℃, resin (e) has a molecule f; (6000, hydroxyl value 20 KOHrng/y,
A polyester resin having a glass transition point of 20°C was obtained.

Regarding Example 1 - polyester resin (a) - eJ, each of the resins was 0
70 parts of toluene was added to the solution, and to this was added 70 parts of toluene and 70 parts of toluene.
An adhesive composition was prepared by adding 15 parts of R-20 (chlorine content of 6496 or more) and 5 parts of Coronet 1 (L (hexamethylene diisocyanate compound)).

Coat this on a vinyl chloride sheet to a thickness of VC5 nol,
After volatilizing the solvent, place polypropylene synthetic paper (paper with polypropylene resin inside) and press under 1 short press.
Bonding was performed at a temperature of 120° C. for 50 minutes. Also, when a polypropylene film was placed on a vinyl chloride sheet, lamination was carried out in the same manner. Table 1 shows the results of examining the adhesive strength and presence or absence of tack for each adhesive.

Comparative Example 1 - Resin instead of polyester resin (A)), (E),
The performance of the adhesive composition was evaluated in the same manner as in Example 1 except that (f) was used. The results are also shown in Table 1.

Comparative Examples 4 to 6 Polyester resins (a), (b), and (c) were dissolved by adding 50 parts of each of the resins and 70 parts of K + -luene, and adding 5 parts of the same isocyanate compound f as in Example 1 on fire. The mixture was mixed to form an adhesive composition. Hereinafter, the composition will be described in Example 1.
Performance evaluation was performed in the same manner. The results are also shown in Table 1.

Example 4 Evaluation was carried out in the same manner as in Example IQ except that 5 parts of Needle Coronate L (Japanese Boricreta) was added as the incyanate compound. The results are shown in Table 1.

Evaluation was carried out using the following method.

In the case of lamination of polyvinyl chloride, polyvinyl chloride, and polypropylene synthetic paper, the judgment was made based on whether or not the polypropylene non-synthetic paper would break when the laminated vinyl chloride sheet base material was exposed to T-beer [7].

In the case of vinyl chloride sheet-polypropylene film, the T-beer strength of the bonded vinyl chloride sheet base material was measured by autograph. (Measurement conditions are temperature 20°C, speed 100 l/min) Tack presence: After applying adhesive to the base material and volatilizing the solvent, place it in a 40'C constant vortex bath and chlorinate the base material. A vinyl sheet was placed on it, and then a pressure of 20 Δd was applied and the degree of blocking was observed after 24 hours.

Table 1 Note: Regarding the adhesive strength of vinyl chloride/polypropylene synthetic paper, the tack

Claims (1)

[Scope of Claims] A polyester resin in which 20 to 80 mol% of the acid component is composed of isophthalic acid, a hydroxyl value of 12 to I 8 KOHwf, and a peacetime average molecular weight of 6,000 to +0,000; An adhesive composition comprising 25% to 50% by weight of an isocyanate compound and 25 to 50% by weight of chlorinated rubber.