CN104130737B - Polyester-polyamide hot-melt adhesive composition and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of polyester-polyamide hot-melt adhesive composition and preparation method thereof.Said composition comprises the carbodiimide compound of the polyester hot-melt adhesive of 60-90 weight part, the polyamide hot of 10-40 weight part and 1-8 weight part.Polyester-polyamide hot-melt adhesive composition of the present invention has second-order transition temperature and hardness is low, flexibility and oil-proofness is good, use temperature wide ranges and the good advantage of adhesiveproperties.

Description

Polyester-polyamide hot-melt adhesive composition and preparation method thereof

technical field

The invention relates to a hot-melt adhesive composition and its application, in particular to a polyester-polyamide hot-melt adhesive composition and its application.

current technology

Hot-melt adhesive is a kind of adhesive that is solid at room temperature and liquid after heating and melting. After being applied to the adherend, it can be bonded and bonded in a short time after being pressed and cooled. Polyester hot melt adhesive is an environmentally friendly and pollution-free green adhesive. In addition to the common advantages of hot melt adhesives such as no chemical solvents and no pollution, it also has high bonding strength and a wide range of bonding materials. The bonding performance of the fiber material is very outstanding, and it has excellent electrical properties, oil resistance and other characteristics, so it has broad development prospects in many application fields.

However, most polyester hot-melt adhesives have the problem of poor flexibility at low temperatures, especially high-melting polyester hot-melt adhesives, which have high hardness and generally have a high glass transition temperature (Tg>-5°C). It is easy to be brittle, thus limiting the development and use in some fields. For example, with the development of low-carbon environmental protection economy, people began to use the cleaning method to prolong the service life of the air filter in the car. They need one that can resist oil (gasoline) and have a lower glass transition temperature ( Tg<-20C), a hot melt adhesive product with good flexibility. This product expands the environmental use range of the material, promotes the adhesive performance of the glue to the substrate, and has good adhesion to various materials such as paper and fabric.

Contents of the invention

The object of the present invention is to provide a polyester-polyamide hot melt adhesive composition. The composition has a lower glass transition temperature, low hardness, good flexibility, good material oil resistance, wide service temperature range and good bonding performance.

The polyester-polyamide hot-melt adhesive composition of the present invention comprises 60-90 parts by weight of polyester hot-melt adhesive, 10-40 parts by weight of polyamide hot-melt adhesive and 1-8 parts by weight of carbodiimide compound.

The preparation method of polyester-polyamide hot-melt adhesive composition of the present invention comprises the steps:

a) mixing polyester hot melt adhesive, dimer acid type polyamide hot melt adhesive and compatibilizer carbodiimide to form a mixture,

b) Melting and extruding the compound to obtain the desired product.

The polyester-polyamide hot-melt adhesive composition of the invention has the advantages of low glass transition temperature and hardness, good flexibility and oil resistance, wide service temperature range and good bonding performance.

Detailed ways:

In a preferred embodiment, the polyester-polyamide hot-melt adhesive composition of the present invention comprises 65-85 parts by weight of polyester hot-melt adhesive, 15-35 parts by weight of polyamide hot-melt adhesive and 1-7 parts by weight Parts of carbodiimide compound:

The polyester hot-melt adhesives used in the present invention include aliphatic polyamide hot-melt adhesives, aromatic polyamide hot-melt adhesives, or mixtures thereof. For example, the polyester hot melt adhesive used in the present invention is a polycondensation reaction product of a dibasic acid component and a _C2-6 diol component. Described dibasic acid component comprises aliphatic dibasic acid component, aromatic dibasic acid component or their mixture, preferably comprises aromatic dibasic acid and optional C _4-12 aliphatic dibasic acid component .

The above-mentioned aromatic dibasic acid includes terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid or their mixtures, preferably includes terephthalic acid, isophthalic acid or their mixtures.

The above-mentioned aliphatic dibasic acid is preferably a C _4-12 aliphatic dibasic carboxylic acid, more preferably a C _4-8 aliphatic dibasic carboxylic acid.

Examples of _C4-12 aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecamethylenedicarboxylic acid and Dodecamethylene dicarboxylic acid or mixtures thereof, preferably succinic acid, adipic acid, suberic acid, sebacic acid or mixtures thereof, more preferably succinic acid, adipic acid and sebacic acid .

The aforementioned dicarboxylic acids may also be replaced by their C _1-4 alkyl esters. Examples of these _C1-4 alkyl esters include dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dimethyl isophthalate , diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, dimethyl adipate, dibutyl adipate, dimethyl pimelate, dipimelate Butyl ester, dimethyl suberate, dibutyl suberate, dimethyl azelate, dibutyl azelate, dimethyl sebacate, dibutyl sebacate, dodecamethylene Dimethyl dicarboxylate, dibutyl dodecamethylene dicarboxylate or mixtures thereof. Preferred are dimethyl terephthalate, dimethyl isophthalate, dimethyl adipate, dimethyl suberate, dimethyl sebacate or mixtures thereof.

The above-mentioned _C2-6 glycol component, for example, includes at least one selected from ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol and triethylene glycol glycol. The above-mentioned dihydric alcohols may be used alone or in combination of two or more.

The number average molecular weight Mn of the polyester hot-melt adhesive resin suitable for the present invention is generally 10,000-100,000, preferably 10,000-80,000.

The melt viscosity (200° C.) of the polyester hot-melt adhesive resin suitable for the present invention is generally 20,000-100,000 mPa.s, preferably 20,000-80,000 mPa.s.

The softening point of the polyester hot-melt adhesive resin suitable for the present invention is generally 100-200°C, preferably 130-190°C.

The polyamide hot-melt adhesive used in the present invention is preferably dimer acid type polyamide hot-melt adhesive. The dimer acid type polyamide hot melt adhesive preferably contains unsaturated aliphatic dimer acid polymerized units and polyamine polymerized units. The polyamine polymerized units consist of at least one of C _2-18 aliphatic diamines.

The above-mentioned unsaturated aliphatic dimer acid polymer units are dimer acid polymer units of C _16-20 unsaturated fatty acids, for example, dimer linoleic acid, dimer oleic acid, dimer linolenic acid, dimer elaidic acid , polymerized units derived from dimerized soyoleic acid and dimerized oleic acid. Preferred are polymerized units of dimer acids derived from C ₁₈ unsaturated fatty acids, for example, polymerized units derived from dimerized linoleic acid, dimerized oleic acid, dimerized linolenic acid, dimerized elaidic acid, dimerized soyoleic acid.

The dimer acid content of the dimer acid type polyamide hot melt adhesive used in the present invention is preferably more than 65wt%, more preferably 75-95wt%, and the triacid content is preferably below 15wt%, more preferably 3-10wt%; It is preferably below 5wt%, and more preferably the content is 1-3wt%.

In a preferred embodiment, a part of dimer acid type polymerized units can be replaced by C _6-12 aliphatic dicarboxylic acid units, preferably replaced by C _6-10 aliphatic dicarboxylic acid units. The added amount of C _6-12 aliphatic dicarboxylic acid units is preferably no more than 40% of the total moles of dimer acid polymerized units, preferably no more than 30%.

The above-mentioned C _6-12 aliphatic dicarboxylic acid unit is derived from a C _6-12 aliphatic dicarboxylic acid. C _6-12 aliphatic dicarboxylic acids include, for example, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid or mixtures thereof, preferred examples include suberic acid, sebacic acid, decadioic acid, Dioxanedioic acid or mixtures thereof. A more preferred example is sebacic acid.

The polyamine polymerized unit in the present invention includes at least one of C _2-18 aliphatic diamine and polyether amine.

Examples of the aforementioned aliphatic diamines include ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, hexamethylenediamine, octyldiamine, dodecanediamine, heterocyclic diamine, Amines such as piperazine, toluenediamine, pyridinediamine and mixtures thereof, preferred examples include C _2-8 aliphatic diamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, piperazine or their A more preferred example is ethylenediamine.

The above polyether polyamine polymer units are derived from polyether polyamines. Polyether polyamines include polyethers with 2-5, preferably 2-3, terminal amino groups, and the molecular weight is generally 150-2500, preferably 200-2000.

The number average molecular weight Mn of the polyamide hot-melt adhesive resin suitable for the present invention is generally 5,000-50,000, preferably 10,000-40,000.

The glass transition temperature of the polyamide hot-melt adhesive resin suitable for the present invention is generally ≤-20°C, ≤-30°C, more preferably ≤-40°C.

The melt viscosity (200° C.) of the polyamide hot-melt adhesive resin suitable for the present invention is generally 5,000-50,000 mPa.s, preferably 10,000-30,000 mPa.s.

The softening point of the polyamide hot-melt adhesive resin suitable for the present invention is generally 100-200°C, preferably 130-190°C.

Compatibilizer carbodiimide compounds used in the present invention may include monomeric carbodiimides, polycarbodiimides, or mixtures thereof. It is a compound containing the -N=C=N- group. Preferred are polycarbodiimide compounds. When polyester hot melt adhesive is added to polyamide hot melt adhesive for blending, the polycarbodiimide compound containing more than two carbodiimide groups plays a good role as a compatibilizer. reaction, on the other hand, it can react with the free amine groups in the polyamide, so as to obtain a hot melt adhesive composition with excellent performance.

The aforementioned carbodiimide compounds are commercially available. At present, there are more Stabaxol-1, Stabaxol–P, Stabaxol–P100, Stabaxol–P200 series products of German Lanxess Rhein Chemie, which are widely used in the domestic market.

In addition to the above-mentioned polyester hot melt adhesive, polyamide hot melt adhesive and carbodiimide compound, the polyester-polyamide hot melt adhesive composition of the present invention can also contain conventional additives in the art, such as anti-aging agents, anti-aging agents, etc. Oxygen, filler, antistatic agent or their mixture. The anti-aging agent used in the present invention is preferably various commercially available amine anti-aging agents, especially aromatic amine anti-aging agents, for example including but not limited to phenylenediamine or naphthalene diamine disubstituted by aryl, preferably Phenyl or naphthyl disubstituted phenylenediamine or naphthalene diamine, more preferably phenylenediamine disubstituted by phenyl or naphthyl. The most preferred specific examples are N,N'-diphenyl-p-phenylenediamine, 4,4'-bis(4-α,α-dimethylbenzyl)diphenylamine, N,N'-di-β- Naphthyl-p-phenylenediamine, or their mixtures.

The preferred preparation method of the polyester-polyamide hot-melt adhesive composition of the present invention comprises the following steps: adding the dried polyester hot-melt adhesive and the dimer acid type polyamide hot-melt adhesive into a V-shaped mixer, and then adding the phase The compatibilizer carbodiimide compound and aromatic amine anti-aging agent are mixed for 5-10 minutes to obtain a mixture. The mixture is melt-extruded through a screw extruder, water-cooled, and pelletized to obtain a polyester-polyamide hot-melt adhesive composition.

The above-mentioned screw extruder includes a single-screw extruder and a twin-screw extruder, and the temperature of melt extrusion is 1-20°C higher than the melting point of the polyester hot melt adhesive, preferably 5-15°C higher.

The obtained polyester-polyamide hot-melt adhesive composition of the present invention, compares with polyester hot-melt adhesive, has lower glass transition temperature, lower hardness and melting viscosity, and dimer acid polyamide hot-melt adhesive In comparison, the oil resistance is good (especially gasoline resistance), and the polyamide hot melt adhesive with matching temperature is selected for blending. The melting point of the obtained polyester-polyamide hot melt adhesive composition is not affected in any way, and the bonding performance is good.

In order to further illustrate the technical effects of the present invention, the following examples will be used to illustrate.

The mensuration and evaluation method of each index of the present invention are as follows:

Melting point test method: on the 823e thermal analysis instrument of Mettler, Switzerland, according to GB/T19466.3-2004 "Plastic Differential Scanning Calorimetry (DSC) Part 3: Determination of Melting and Crystallization Temperature and Enthalpy" Determination.

Melt viscosity test method: Accurately weigh 10g polyester-polyamide hot melt adhesive composition sample, dry the moisture in an oven, and use BrookfieldDV-Ⅱ+Pro type rotational viscometer to test, test temperature 200～232℃, rotor number S27, record the melt viscosity value displayed on the dial after the rotor starts to rotate for 30 minutes, and adjust the speed according to the actual situation.

The test method of glass transition temperature: on the 823e thermal analysis instrument of Swiss Mettler company, according to GB/T19466.2-2004 "Plastic Differential Scanning Calorimetry (DSC) Part 2: Determination of Glass Transition Temperature" stipulated.

Determination of hardness: refer to GB/T531.1 and GB/T531.2 test.

T-peel strength: apply the polyester-polyamide hot melt adhesive composition on the surface of cotton fabric with a width of 15mm, the amount of glue used is about 40g/ ^m2 , compound another cotton fabric, and place it under the test condition for 12h Finally, the peel performance test is carried out on a model GT-AI-3000 tensile testing machine.

Oil resistance test: The polyester-polyamide hot melt adhesive composition is made into a 50×20×4 mm sheet, the initial weight is recorded, and immersed in gasoline at room temperature for 96 hours. According to the test basis of the corrosion performance of copolymerized polymer materials, it is stipulated that the swelling is less than 5% as excellent, more than 20% is dissolved and destroyed, and the middle is swelling. Test results G stands for insoluble (weight change ≤ 5%), E stands for swelling (weight change > 5%, ≤ 10%), E+ stands for swelling (weight change > 10%, ≤ 15%), E++ stands for swelling ( Weight change > 15%, ≤ 20%), F stands for dissolution.

Example

Example 1

70 parts by weight of polyester hot melt adhesive (brand LR-PES-185, purchased from Shanghai Liri Chemical New Material Co., Ltd., melting point 172°C, melt viscosity 30600mPa.s/232°C), polyamide hot melt adhesive (brand LR -ZSB-180, purchased from Shanghai Liri Chemical New Material Co., Ltd., softening point: 182°C, melt viscosity: 15600mPa.s/200°C, glass transition temperature: -40°C) 30 parts by weight, in an oven at 105°C After drying in medium for 4 hours, with 3 parts by weight of polycarbodiimide (brand Stabaxol–P200, from Lanxess Rhein Chemie) and 2 parts by weight of 4,4'-bis(4-α,α-dimethyl Benzyl)diphenylamine (brand name KY405 purchased from Jiangsu Feiya Chemical Industry Co., Ltd.) was mixed in a V-type mixer for 5 minutes, then added to a twin-screw extruder at 185°C for melt blending, extrusion, water cooling, and cutting pellets to obtain a polyester-polyamide hot-melt adhesive composition. The various indicators of the test composition are shown in Table 1.

Example 2-6

The following five examples are carried out in the same steps and methods as in Example 1, except that the raw material, polycarbodiimide amount and melt extrusion temperature are shown in Table 1 below, and the analysis results of the resulting product are also listed in the table 1 in.

Table 1 Examples 1-6

Table 2 above-mentioned polyester, polyamide hot-melt adhesive monomer performance index

It can be seen from the above Tables 1 and 2 that in Examples 1-6, carbodiimide is used as a compatibilizer, so that polyester and polyamide have good compatibility, thereby obtaining a hot melt adhesive combination with excellent performance things. Compared with polyester hot melt adhesives, it has lower glass transition temperature, lower hardness and melt viscosity. Compared with dimer acid polyamide hot melt adhesives, it has better oil resistance (especially gasoline resistance), and the selection temperature The matching polyamide hot-melt adhesive is blended, and the melting point of the obtained polyester-polyamide hot-melt adhesive composition is not affected in any way, and the bonding performance is good.

Claims (8)

1. A polyester-polyamide hot-melt adhesive composition, which comprises the polyester hot-melt adhesive of 60-90 parts by weight, the dimer acid type polyamide hot-melt adhesive of 10-40 parts by weight and 1-8 parts by weight The carbodiimide compound, the number average molecular weight Mn of the polyester hot melt adhesive is 10,000-100,000, and the number average molecular weight Mn of the dimer acid polyamide hot melt adhesive is 5,000-50,000. 2. polyester-polyamide hot-melt adhesive composition as claimed in claim 1, it comprises the polyester hot-melt adhesive of 65-85 weight part, the dimer acid type polyamide hot-melt adhesive of 15-35 weight part and 1-7 parts by weight of carbodiimide compound. 3. The polyester-polyamide hot-melt adhesive composition according to claim 1, characterized in that the number average molecular weight Mn of the polyester hot-melt adhesive is 10,000-80,000. 4. The polyester-polyamide hot-melt adhesive composition according to claim 1, wherein the number average molecular weight Mn of the dimer acid type polyamide hot-melt adhesive is 10,000-40,000. 5. polyester-polyamide hot-melt adhesive composition as claimed in claim 1 or 2, is characterized in that, described carbodiimide compound comprises monomer carbodiimide, polycarbodiimide or their mixture. 6. The polyester-polyamide hot-melt adhesive composition as claimed in claim 1 or 2, characterized in that it also comprises 0.5-3 parts by weight of an anti-aging agent. 7. The polyester-polyamide hot-melt adhesive composition as claimed in claim 6, wherein said anti-aging agent is an amine anti-aging agent. 8. the preparation method of polyester-polyamide hot-melt adhesive composition as described in any one in claim 1-7, it comprises the steps: a) mixing polyester hot melt adhesive, dimer acid type polyamide hot melt adhesive and compatibilizer carbodiimide to form a mixture, b) Melting and extruding the mixture.