Anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods and preparation method of anti-swelling hot-melt pressure-sensitive adhesive

Abstract

The invention relates to the field of adhesives, in particular to the field of C09J155 / 00, and more particularly relates to an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast moving consumer goods and a preparation method of the anti-swelling hot-melt pressure-sensitive adhesive. The anti-swelling hot-melt pressure-sensitive adhesive is prepared from the following raw materials in parts by mass: 30 to 40 parts of styrene-containing segmented copolymer, 40 to 60 parts of resin, 10 to 35 parts of petrochemical fractionation oil, 5 to 20 parts of tackifier and 0.5 to 1.5 parts of additive. The anti-swelling hot-melt pressure-sensitive adhesive provided by the invention has excellent initial adhesion performance and persistent adhesion performance, is peelable, does not need to use an additional organic solvent in preparation, and is simple in whole preparation process, relatively low in cost and green and environment-friendly.

Description

Technical Field

[0001] The present invention relates to the field of adhesives, in particular to the field of C09J155 / 00, and more specifically to an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods and a preparation method thereof. Background Art

[0002] Film tape is a tape product made of film material as the base material and coated with adhesive. Film tape has a wide range of uses and is widely used in packaging, printing, electronics, home furnishing and other fields. Film tape can be divided into many types according to the different base materials; however, when PP, PVC, BOPP, POF and other materials are used as the film base material, after ordinary hot-melt pressure-sensitive adhesive is used to coat the tape, the polymer on its surface will come into contact with moisture or other solvents in the air after being placed for a period of time, and then it will swell; although the swollen polymer can better contact with the surface of the base material and form a tighter bonding interface, the movement of the polymer chain segments during the swelling process also helps to remove air and impurities between the interfaces and improve the bonding strength; however, swelling will cause the volume of the adhesive layer to increase and the density to decrease, thereby affecting the product's performance and storage stability.

[0003] Prior art CN112680131A discloses a PVC-based UV anti-viscosity adhesive film for semiconductor chip inversion and its preparation method. The raw materials for preparing the glue include acrylic glue, UV monomer or oligomer. The glue has high stability and no residue after coating. It is well known that acrylic glue is superior to hot-melt pressure-sensitive adhesive in terms of both material and processing technology, and is also better than hot-melt pressure-sensitive adhesive in terms of weather resistance. However, the initial adhesion and sustained adhesion performance of hot-melt pressure-sensitive adhesive are more excellent, and hot-melt pressure-sensitive adhesive is more environmentally friendly than acrylic glue because it is solvent-free. In addition, specifically combined with the application of fast-moving consumer goods, fast-moving consumer goods generally do not have a long service life. Therefore, compared with acrylic glue, hot-melt pressure-sensitive adhesive is obviously more suitable for the bonding of fast-moving consumer goods. Summary of the invention

[0004] In order to solve the above technical problems, the first aspect of the present invention provides an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods. The raw materials include, by weight: 30-40 parts of styrene block copolymer, 40-60 parts of resin, 10-35 parts of petrochemical distillation oil, 5-20 parts of tackifier, and 0.5-1.5 parts of additive.

[0005] Preferably, the styrene-containing block copolymer includes: styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS) or a combination of the two.

[0006] Further preferably, the styrene-containing block copolymer comprises SBS and SIS, and the mass ratio of the two is (2-5):1.

[0007] Further preferably, the mass fraction of styrene in the styrene-isoprene-styrene block copolymer (SIS) is 15-30%, and the melt flow rate at 200°C is 10-15 g / 10 min; as an implementable case, the brand of the SIS is selected from one of YH-1209 or YH-1126, both of which are purchased from Yueyang Petrochemical; the mass fraction of styrene in YH-1209 is 29%, and the melt flow rate at 200°C is 12 g / 10 min; the mass fraction of styrene in YH-1126 is 16%, and the melt flow rate at 200°C is 10 g / 10 min.

[0008] Further preferably, the mass fraction of styrene in the styrene-butadiene-styrene block copolymer (SBS) is 25-35%, the melt flow rate at 200°C is 4-11g / 10min, and the heat deformation temperature is <90°C; as an implementable case, the brand of the SBS is selected from YH-188, purchased from Yueyang Petrochemical.

[0009] SIS and SBS are both thermoplastic elastomers with similar block copolymer structures, but the rubber phase (isoprene and butadiene) in the middle block is different. This structural difference makes SIS and SBS complementary in performance. When they are compounded, they can form a tighter network structure through intermolecular interaction and entanglement, thereby enhancing the cohesion and stability of the material and reducing solvent penetration and swelling.

[0010] SBS and SIS with a high styrene content have an increased rigid segment ratio, which enhances the interaction between molecular chains and makes the material more compact. This compact structure makes it difficult for solvent molecules to penetrate into the interior of SBS, thereby reducing the degree of swelling. On the contrary, SBS with a low styrene content has a high flexible segment ratio, weaker interaction between molecular chains, and more easily penetrates into the material, resulting in an increase in the degree of swelling; however, too high a styrene content will cause the fluidity of SBS and SIS to decrease, and the processing performance will deteriorate. Therefore, YH-1209 and YH-188 are preferred in the present invention, which can ensure that the anti-swelling hot-melt pressure-sensitive adhesive has certain anti-swelling properties, and the processing performance of the anti-swelling hot-melt pressure-sensitive adhesive is guaranteed.

[0011] Preferably, the resin includes petroleum resin and rosin resin.

[0012] Further preferably, the petroleum resin includes one or more of hydrogenated C5 petroleum resin, C5 petroleum resin, hydrogenated C9 petroleum resin, and C9 petroleum resin.

[0013] More preferably, the petroleum resin is hydrogenated C5 petroleum resin, with a softening point of 100-120° C. and a yellowness index of ≤4.5; as an implementable case, the hydrogenated C5 petroleum resin is brand H5-1000 of Henghe Materials.

[0014] Further preferably, the rosin resin includes modified rosin resin, the softening point (ring and ball method) of the modified rosin resin is 95-110° C., and the acid value is 40-50 mg KOH / g; as an implementable case, the modified rosin resin brand includes Kohler resin 146, which has a softening point (ring and ball method) of 99-107° C. and an acid value of 40 mg KOH / g.

[0015] The present invention adopts YH-1209 and YH-188 to work together to prepare an anti-swelling hot melt pressure-sensitive adhesive with good aging resistance. After adding hydrogenated C5 petroleum resin, it is applied to the anti-swelling hot melt pressure-sensitive adhesive, the compatibility between the raw materials is good, and the anti-swelling performance is further improved. Possible reasons are speculated to be: the butadiene block in the linear SBS and the isoprene block in the SIS are cross-linked by covalent bonds to form mutually penetrating entangled chain segments, so that the two main polymers are combined together to form a cross-linked network; the hydrogenated C5 petroleum resin has been hydrogenated to remove the unsaturated bonds in the molecule, thereby improving the thermal stability and antioxidant properties of the body, and further enhancing the bonding effect of the hot melt pressure-sensitive adhesive; however, the hydrogenated C5 petroleum resin has a low polarity, and the adhesive layer is prone to warping during use. Therefore, the present invention adds a highly polar modified rosin resin to avoid the warping of the adhesive layer. At the same time, the modified rosin resin can achieve an optimal balance between tearability and adhesion, which not only ensures the tearability of the anti-swelling hot melt pressure-sensitive adhesive, but also improves its initial adhesion, meeting the needs of fast-moving consumer goods.

[0016] Preferably, the petrochemical fractionated oil is selected from naphthenic oil and / or white mineral oil.

[0017] Further preferably, the petrochemical distillation oil is cycloparaffinic oil, and the kinematic viscosity of cycloparaffinic oil at 40°C is 120-140 cSt; as an implementable case, the cycloparaffinic oil is grade 4010, purchased from PetroChina.

[0018] The addition of cyclopentane oil not only improves the fluidity and plasticity of the anti-swelling hot melt pressure-sensitive adhesive, but also significantly enhances its bonding performance and water resistance. By enhancing the interaction between the anti-swelling hot melt pressure-sensitive adhesive and the bonded material, the bonding interface is made more firm and durable. At the same time, it can also effectively prevent moisture from penetrating into the anti-swelling hot melt pressure-sensitive adhesive, reduce the aging and hardening degree of the glue, and further improve the anti-swelling performance of the product; however, when the viscosity of the cyclopentane oil is too high, the fluidity of the glue will be significantly reduced, which will cause the anti-swelling hot melt pressure-sensitive adhesive to be difficult to evenly distribute on the surface of the adherend during the coating or gluing process, affecting the bonding effect. Therefore, the present invention preferably uses cyclopentane oil with a kinematic viscosity of 120-140 cSt at 40°C as petrochemical fractionated oil.

[0019] Preferably, the tackifier comprises polyisobutylene, and the number average molecular weight of the polyisobutylene is 350-3500.

[0020] More preferably, the number average molecular weight of the polyisobutylene is 1300, and the brand is Korea Dalin PB1300.

[0021] Preferably, the auxiliary agent includes: one or more of an anti-ultraviolet agent, an antioxidant, a high temperature resistant auxiliary agent, and a high humidity environment adhesion agent; as a preferred embodiment, the auxiliary agent is an antioxidant, and the antioxidant is antioxidant 1010 purchased from Lianlong.

[0022] The second aspect of the present invention provides a method for preparing an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods, comprising:

[0023] S1. First, put petrochemical fractionated oil and 1-99% of the total mass of tackifier into a stirred kettle, stir and heat until the temperature reaches 110-120°C, then add styrene block copolymer, heat to 130-140°C and stir to melt;

[0024] S2. Add resin, additives and the remaining tackifier, and when the temperature of the material rises to 130-140°C, evacuate and continue stirring for 30-40 minutes, extrude, and the material is ready.

[0025] Beneficial Effects

[0026] (i) The anti-swelling hot-melt pressure-sensitive adhesive prepared by the present invention has better bonding performance and peelability than the common acrylic glue on the market, and is particularly suitable for use in fast-moving consumer goods.

[0027] (ii) The specific styrene-containing block copolymer compound selected in the present invention not only ensures that the anti-swelling hot-melt pressure-sensitive adhesive has excellent bonding properties, but also ensures that the product has good anti-swelling properties.

[0028] (III) In order to further improve the bonding performance of the anti-swelling hot melt pressure-sensitive adhesive, the present invention selects hydrogenated C5 petroleum resin with specific parameters. At the same time, since the hydrogenated C5 petroleum resin has undergone hydrogenation processing and does not include unsaturated bonds in the molecule, the thermal stability, oxidation resistance and anti-swelling performance of the product are also improved.

[0029] (IV) In order to avoid the warping problem of the anti-swelling hot-melt pressure-sensitive adhesive caused by hydrogenated C5 petroleum resin, the present invention adds a certain amount of highly polar modified rosin resin to the preparation system, which can improve the initial adhesion and stability of the anti-swelling hot-melt pressure-sensitive adhesive and avoid the occurrence of warping after application.

[0030] (V) The preparation method of the present invention is relatively simple. It can be prepared by simply adding the various preparation raw materials into the reaction system in a certain order at a certain temperature. No additional organic solvent is needed. The entire preparation process is simple, low in cost, and green and environmentally friendly. DETAILED DESCRIPTION

[0031] Example 1

[0032] In the first aspect of this example, an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods is provided. The raw materials include, by weight: 32 parts of styrene block copolymer, 43 parts of resin, 14.5 parts of petrochemical distillation oil, 10 parts of tackifier, and 0.5 parts of auxiliary agent.

[0033] The styrene-containing block copolymer is SIS and SBS, and the mass ratio of the two is 1:3, wherein the brand of SIS is Yueyang Petrochemical YH-1209 (the mass fraction of styrene is 29%, and the melt flow rate at 200°C is 12g / 10min), and the brand of SIS is Yueyang Petrochemical YH-188 (the mass fraction of styrene is 32%, the melt flow rate at 200°C is 6g / 10min, and the heat deformation temperature is less than 90°C).

[0034] The resin is hydrogenated C5 petroleum resin and modified rosin resin, and the mass ratio of the two is 1:1; the brand of hydrogenated C5 petroleum resin is Henghe Material H5-1000 (softening point is 100°C, yellow index ≤4.5), and the brand of modified rosin resin is Kohler Resin 146 (softening point (ring and ball method) 99-107°C, acid value is 40mg KOH / g).

[0035] The petrochemical fractionated oil is naphthenic oil with a brand of 4010 (kinematic viscosity at 40° C. is 140 cSt) purchased from PetroChina.

[0036] The tackifier is polyisobutylene, and the brand is Korea Dalin 1300 (number average molecular weight 1300).

[0037] The auxiliary agent is antioxidant 1010, purchased from Lionlon.

[0038] The second aspect of this example provides a method for preparing an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods, comprising:

[0039] S1. First, put petrochemical fractionated oil and 5 parts of tackifier into a stirring kettle, stir and heat until the temperature reaches 120°C, then add SBS and SIS in sequence, heat to 135°C and stir to melt;

[0040] S2. Add resin and the remaining tackifier and additives, raise the temperature, and when the material reaches 130°C, evacuate and continue stirring for 30 minutes, extrude, and discharge the material.

[0041] Comparative Example 1

[0042] In the first aspect of this example, an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods is provided. The raw materials include, by weight: 32 parts of styrene block copolymer, 43 parts of resin, 14.5 parts of petrochemical distillation oil, 10 parts of tackifier, and 0.5 parts of auxiliary agent.

[0043] The styrene-containing block copolymer is SIS and SBS, and the mass ratio of the two is 1:3, wherein the brand of SIS is Yueyang Petrochemical YH-1209 (the mass fraction of styrene is 29%, and the melt flow rate at 200°C is 12g / 10min), and the brand of SIS is Yueyang Petrochemical YH-188 (the mass fraction of styrene is 32%, the melt flow rate at 200°C is 6g / 10min, and the heat deformation temperature is less than 90°C).

[0044] The resin is hydrogenated C5 petroleum resin, and the brand is Henghe Material H5-1000 (softening point is 100° C., yellow index ≤4.5).

[0045] The petrochemical fractionated oil is naphthenic oil with a brand of 4010 (kinematic viscosity at 40° C. is 140 cSt) purchased from PetroChina.

[0046] The tackifier is polyisobutylene, and the brand is Korea Dalin 1300 (number average molecular weight 1300).

[0047] The auxiliary agent is antioxidant 1010, purchased from Lionlon.

[0048] The second aspect of this example provides a method for preparing an anti-swelling hot-melt pressure-sensitive adhesive suitable for fast-moving consumer goods, comprising:

[0049] S1. First, put petrochemical fractionated oil and 5 parts of tackifier into a stirring kettle, stir and heat until the temperature reaches 120°C, then add SBS and SIS in sequence, heat to 135°C and stir to melt;

[0050] S2. Add resin and the remaining tackifier and additives, raise the temperature, and when the material reaches 130°C, evacuate and continue stirring for 30 minutes, extrude, and discharge the material.

[0051] Performance Evaluation

[0052] Test method: The substrate is PP synthetic film and the glue coating amount is 30±5gsm.

[0053] 180° peel strength: Refer to standard GB / T 2792-2014 Test method for peel strength of adhesive tape.

[0054] Ring tack: Refer to standard GB / T 31125-2014 Adhesive tape initial tack test method (ring method).

[0055] Stickiness: Refer to the test method for stickiness of adhesive tapes in standard GB / T 4851-2014.

[0056] The test results are shown in Table 1. The anti-swelling hot-melt pressure-sensitive adhesive prepared in Comparative Example 1 warped after coating and was not very practical, so Example 1 was used as the test object.

[0057] Table 1

[0058] Test items Example 1 <![CDATA[Ring tack N / in 2 > 22 180° peel force N / in 17 Stickiness hrs / 1kg 14

Claims

1. An anti-swelling hot melt pressure-sensitive adhesive suitable for fast-moving consumer goods, characterized in that: The raw materials include, by weight: 30-40 parts of styrene block copolymer, 40-60 parts of resin, 10-35 parts of petrochemical fractionated oil, 5-20 parts of tackifier, and 0.5-1.5 parts of auxiliary agent.

2. The anti-swelling hot-melt pressure-sensitive adhesive according to claim 1, characterized in that: The styrene-containing block copolymer includes: styrene-ethylene-butylene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-isoprene-styrene block copolymer or a combination of several thereof.

3. The anti-swelling hot-melt pressure-sensitive adhesive according to claim 2, characterized in that: The styrene-containing block copolymer comprises SBS and SIS, and the mass ratio of the two is (2-5):

1.

4. The anti-swelling hot-melt pressure-sensitive adhesive according to claim 2, characterized in that: The mass fraction of styrene in the styrene-isoprene-styrene block copolymer is 15-30%, and the melt flow rate at 200°C is 10-15g / 10min; the mass fraction of styrene in the styrene-butadiene-styrene block copolymer is 25-35%, and the melt flow rate at 200°C is 4-11g / 10min, and the heat deformation temperature is less than 90°C.

5. The anti-swelling hot melt pressure-sensitive adhesive according to any one of claims 1 to 4, characterized in that: The resin includes petroleum resin and rosin resin.

6. The anti-swelling hot-melt pressure-sensitive adhesive according to claim 5, characterized in that: The petroleum resin includes one or more of hydrogenated C5 petroleum resin, hydrogenated C9 petroleum resin, C5 petroleum resin and C9 petroleum resin.

7. The anti-swelling hot-melt pressure-sensitive adhesive according to claim 6, characterized in that: The softening point of the hydrogenated C5 petroleum resin is 100-120° C., and the yellowness index is ≤4.

5.

8. The anti-swelling hot-melt pressure-sensitive adhesive according to claim 1, characterized in that: The tackifier comprises polyisobutylene, and the number average molecular weight of the polyisobutylene is 350-3500.

9. The anti-swelling hot-melt pressure-sensitive adhesive according to claim 1, characterized in that: The auxiliary agent includes: one or more of an anti-ultraviolet agent, a high temperature resistant auxiliary agent, an antioxidant, and a high humidity environment adhesive.

10. A method for preparing the anti-swelling hot melt pressure-sensitive adhesive according to any one of claims 1 to 9, characterized in that: include: S1. First, put petrochemical fractionated oil and 1-99% of the total mass of tackifier into a stirred kettle, stir and heat until the temperature reaches 110-120°C, then add styrene block copolymer, heat to 130-140°C and stir to melt; S2. Add resin, additives and remaining tackifier, and when the temperature of the material rises to 130-140°C, evacuate and continue stirring for 30-40 minutes, extrude and discharge the material.