JPS6026421B2 - Reinforced polyvinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention aims to improve the thermal stability of polyvinyl chloride resin compositions reinforced with talc and the decrease in impact resistance caused by the decrease in thermal stability. The present invention relates to a resin composition.

In recent years, research has been conducted in various fields on combining thermoplastic resins with inorganic fillers to impart mechanical strength and heat resistance, and some have already been put into practical use.

Regarding polyvinyl chloride, reinforcement with glass fibers is known. Other fillers being studied include asbestos, wollastonite, and gypsum fiber. These fibrous fillers are oriented in the flow direction during molding, resulting in anisotropy in physical properties, and have the disadvantage that physical properties in the direction perpendicular to the flow are extremely low. Mica and talc are examples of fillers with low anisotropy, but when mica is filled into polyvinyl chloride, the aspect ratio (ratio of length to thickness) decreases due to the cutting force during molding, resulting in poor reinforcement of physical properties. Furthermore, although talc has stronger physical properties and less anisotropy than mica, it significantly accelerates the deterioration of polyvinyl chloride, causing so-called fading during molding and causing molded products to turn black. Furthermore, when the mixing time of talc and polyvinyl chloride is increased, the thermal stability is further reduced, and as a result, the impact resistance is significantly reduced.

It is generally known that blending inorganic fillers with polyvinyl chloride accelerates the deterioration of the polyvinyl chloride, and the reason for this is said to be that iron ions, etc. contained as impurities accelerate dehydrochlorination of the polyvinyl chloride. ing.

Asbestos-polyvinyl chloride is often used as so-called PVC tiles, but in this case, various studies have been conducted to improve its thermal stability. It is said that dicyandiamide and melamine have a great effect on improving thermal stability. However, even if one part of dicyandiamide or melamine is added to a polyvinyl chloride compound containing talc, the former will not have any further improvement in thermal stability. The inventors have found that the latter has almost no effect.

Further, even if tribasic sulfate or butyltin malate, which has excellent effects as a stabilizer for polyvinyl chloride, is added, the effect is hardly seen. Furthermore, polyamides with a melting point or softening point of about 200°C or less are effective for improving the thermal stability of polyvinyl chloride resin compositions containing talc, but even when their thermal stability is improved, talc and polyamide It has been found that when mixing with vinyl chloride, if the mixing time is increased or a large mixer is used to improve the dispersion of talc, the thermal stability decreases, resulting in a significant decrease in impact strength.

As a result of intensive research, the present inventor has conducted extensive research in order to achieve the above-mentioned objective of improving the thermal stability of a vinyl chloride resin composition containing talc and the decrease in impact resistance caused by the decrease in thermal stability.
When an amide compound represented by R, CONHR2 is added to a vinyl chloride resin containing 15% or less of tungsten in particles of 10 or more, the thermal stability improves, and even if the mixing time is increased, the thermal stability and resistance are improved. They discovered that the decrease in impact resistance was small and arrived at the present invention.

where R, is a saturated or unsaturated aliphatic hydrocarbon, R2 is -C&OR5 or -R3NHCOR4 (R3,
R4 and R5 are each hydrogen or the same or different saturated or unsaturated aliphatic hydrocarbons.

The present invention will be explained in detail below.

Talc used in the present invention has a mineral composition of M&(
A monoclinic mineral represented by Si40,o)(OH)2, which is used in the form of flakes obtained by crushing ore.

When it is desired to improve not only the thermal stability but also the impact resistance as in the present invention, the effect can be fully exhibited by using talc containing 15% or less of particles having 10 or more peaks.

If necessary, talc may be surface-treated with a silane coupling agent, an organic titanate, a fatty acid, etc. before use.
Particles of 10 or more sizes filled in polyvinyl chloride resin are 1
A base of 5% or less talc is optional, but 1% by weight (all percentages hereinafter are by weight).

) or more, preferably 5% or more and 40% or less.
Even if the filler content exceeds 40% or is less than 1%, the impact resistance will be low and the effects of the present invention will not be fully exhibited. The polyvinyl chloride resin referred to in the present invention refers to polyvinyl chloride resin, polypinylidene chloride resin, vinyl chloride, vinylidene chloride copolymer, copolymer of pinyl chloride and vinyl acetate, maleic anhydride, ethylene, propylene, etc. , modified resins such as chlorinated polyvinyl chloride resins, which can be used alone or in combination.

It is also possible to mix resins for improving impact resistance such as ABC, M-silver, and chlorinated polyethylene.

As compounding agents, stabilizers such as lead-based, tin-based, Ca-Zn-based stabilizers, thickeners, and processability improvers can be added. Other fillers as necessary, such as calcium carbonate, gypsum, gypsum fiber,
Asbestos, mica, calcium silicate, glass fiber, etc. may be used in combination. The amide compound of the present invention is R,CONH
In the N amide compound represented by R2, R is a saturated or unsaturated aliphatic hydrocarbon, preferably C. The above saturated or unsaturated aliphatic hydrocarbons. R2 excludes the day -C ratio O
R5 or -R3NHCOR4, R3 is an aliphatic hydrocarbon such as methylene, ethylene, etc., R4, R5 are H or the same or different saturated or unsaturated aliphatic hydrocarbons, preferably the same on C, J〆 or different saturated or unsaturated aliphatic hydrocarbons.

R. To illustrate with CONHCH20R5, methylolated lauric acid amide CH3kiCQna,oCONHCH20
day, methylolated balmitic acid amide CH3 x CH2 na, 4CONHCH20 days, methylolated behenic acid amide CH3 x CH2 na 2.

CONHCH 20 days, methylolated stearic acid amide CH2 x CH2 na, 6CONHCH 20 days, methylolated oleic acid amide △℃, 7 days 8CONHCH 20 days,
Methi.

conjugated erucic acid amide △13C2. day, CONHC horse O
H etc. R, CONHR3NHCOR4 is an example of methylene bislauric acid amide C, . Sun 23 CONH
CH2NHCOC,. H, methylene bisbalmitic acid amide C, rainbow 3, CONHCH2NHCOC, 5th,
Methylene bisstearamide C, 7 days 35CONH
CH2NHC○C, 7H$, ethylene pithlauric acid amide C,. 23rd CONHCH2C is NHCOC,. ratio 3, ethylene pisbalmitic acid amide, C, rainbow 3, CO
NHCH2C ratio NHCOC, 5 melon, ethylene bisstearisoamide C, 7 days 35CONHCH2C4NHC
OC, 7 horses 5, ethylene bisbehenic acid amide C2, day 4
3CONHCH2CMNHCOC2, 53, ethylenebisoleic acid amide △9C, 7 & 3CONHC ratio - C ratio NHCOC△9C, 7 days 33, etc.

Although the method of mixing the amide compound of the present invention is arbitrary,
For example, the amide compound of the present invention may be mixed into polyvinyl chloride during polymerization, the amide compound of the present invention may be added to and mixed with a vinyl chloride resin compound containing talc, or the amide compound of the present invention may be added to talc in advance and mixed with heat, followed by chlorination. There is a method of adding it to vinyl resin compounds. Furthermore, the talc may be surface-treated.

The amount of the amide compound of the present invention to be used is approximately 0.00 parts by weight of 10 parts by weight of talc containing 15% or less of particles with 10 or more peaks.
5 parts by weight to 1 part by weight are preferred.

Regarding the effects of the present invention, the time for mixing talc and polyvinyl chloride resin at high speed (referred to as premixing) with 15% or less of particles having 10 or more peaks was varied from 0, 5, and 1 minutes, and then the stabilizer, Thermal stability is measured by plastograph of a compound obtained by adding a thickening agent, etc., high-speed mixing to 110%, and then cooling, and the DuPont impact strength (hereinafter referred to as DuPont (abbreviated as ), when the amide compound of the present invention is not added, both thermal stability and DuPont value rapidly decrease. It can be seen that this rapid decrease is caused by the formation of polyenes, as the absorption in the infrared absorption spectrum of ~1600 UI increases as the premixing time of the molded product increases.

When the amide compound of the present invention is added, although it depends on the type of compound and the amount used, the decrease in thermal stability and DuPont is small even if the premixing time becomes long, and when the optimum amount is used, the Even with pre-mixing, no decrease in thickness was observed.

In the infrared absorption spectrum, absorption at 1650 h-1 (non-conjugated double bond) is seen, but absorption at 1600 h-1 is small, so the amide compound of this sea bream is a compound of conjugated polyene of polyvinyl chloride resin containing talc. It prevents the generation. That is, although the amide compound of the present invention cannot prevent dehydrochlorination, a unique effect was observed in the presence of talc in that it prevented the conjugation of double bonds generated by dehydrochlorination.

Lead compounds, tin compounds, and other metal salts, which are known as stabilizers for polyvinyl chloride resins, do not have this effect, so they act differently from other stabilizers.

Such an effect is particularly remarkable when the particle size distribution of the talc used is such that particles of 10 μm or more are 15% or less.

If the proportion of particles of 10 μm or more exceeds 15%, the effects of the present invention cannot be sufficiently exhibited because the impact strength of the resulting molded product is inherently low. Among the amide compounds of the present invention, the bisamide represented by R,CONHR3NHCOR4 significantly improves the thermal stability of polyvinyl chloride resin containing talc, but the thermal stability of the compound represented by R,CONHC ratio OR5 is Although it has the effect of not decreasing even if the time is prolonged, in order to further exhibit the effect of increasing thermal stability, the bisamide represented by R, CONHR3NHCOR4 of the present invention or a polyamide with a melting point or softening point of 20 pi○ or less is used. It is preferable to use them together.

The vinyl chloride resin composition of the present invention can be molded by a conventional method after adding necessary additives, but it is preferable that the talc and the pinyl chloride resin are thoroughly mixed.

For example, depending on the machine, the ingredients may be thoroughly mixed using a high-speed mixer (Henschel mixer), or they may be mixed in advance using a Banbury mixer before forming. For molding, there is a method of direct molding using a two-roll, single-screw extruder, twin-screw extruder, special compound kneader, or a method of direct molding using a two-roll, Banbury mixer, single-screw extruder, twin-screw extruder, or special compound kneading machine. Manufacture pellets using a rolling mill,
Injection molding, blow molding, extrusion molding, calendar molding,
The molding material may be obtained by melt spinning processing or the like.

Talc has traditionally been used as a filler for polystyrene and polyolefins, but for pinyl chloride resins, it is used in applications that do not require heat stability, such as in paints, or applications that use large amounts of plasticizers, such as in soft trade. It was hardly ever put into practical use. One of the reasons for this is that the thermal stability is extremely poor, and therefore the impact strength tends to vary, making it difficult to implement industrially.However, the amide compound of the present invention is not a stabilizer, and moreover, Although it is common knowledge that talc decreases the heat resistance of polyvinyl chloride, it has the effect of improving thermal stability in the presence of talc.
Furthermore, it is a novel effect unique to the present invention that thermal stability is less affected by mixing conditions and impact strength decreases less, and its industrial utility value is extremely high.

The present invention will be explained in detail below with reference to Examples.

Example 1 Talc produced in China was crushed and classified using a super micron mill to prepare talc containing 9.6% of 101 or more.

(Table 2) Polyvinyl chloride (trade name, Kanepinil S-
1001) 10 parts of anchor, 1 part of tribasic lead sulfate, 0.5 parts of dibasic stearate, 1.5 parts of stearate
The basic composition is 0.5 parts of calcium stearate, 0.5 parts of barium stearate, and 0.2 parts of polyethylene wax, and 20 parts of talc and polyvinyl chloride are mixed in advance.
Using the super mixer, mix at high speed under water cooling (hereinafter referred to as premixing), then add stabilizers and thickeners, mix at high speed while heating, and as soon as it reaches 110 o'clock, mix at 70 q0.
It is cooled to a temperature of 50% and then discharged to obtain a lead-containing compound.
The content of talc is measured to be 15% in the compound.

Three conditions were used for the premixing time: 0 minutes, 5 minutes, and 10 minutes. To measure the thermal stability of the obtained compound, a kneader-type Plastograph (manufactured by Brabender) with an internal volume of 55 cc was used, and a 73-day compound was charged, the heating time was 4 minutes, and the rotor rotation speed was 3 pm. , chamber temperature 18
I took a plastogram at Pi○.

To explain this using a typical blastogram shown in Figure 1, the times when the torque is 0.1k91m higher than the minimum torque are (Tc) and Tc, respectively.
Let c be the maximum torque generation time TB, the one closest to the maximum torque be (Tc), and the one closest to the maximum torque be (Tc), △T,=
It was defined as Tc-(Tc), ΔT2=Tc-TB. △T
, is the steady torque holding time, and ΔT2 is the time from when the maximum torque is reached until the start of decomposition, both of which are parameters representing thermal stability. For evaluation of impact resistance, the obtained compound was made into pellets using a single screw extruder with a 4W port, and then a belt with a medium length of 60 ships and a thickness of 3 kites was formed using an extruder with a 4 ship rating. Cut x 3 pieces, heat 5 molecules at 180℃, and press for 5 minutes to create a test piece with a thickness of about 2.3cm.・Dupont style scale-ori butazen.Half fracture height in 30M equivalent with notch: 5o (abbreviated as DuPont as mentioned above).

As an example of the present invention, ethylene bisstearylamide (
(hereinafter referred to as E spots) and methylolated stearylamide (hereinafter referred to as MSA) to the above formulation, respectively, at a rate of 0.5 to talc.
%, 1.0%, 1.5%, 5.0%, 10%, ΔT, ΔL, and DuPont were determined and shown in Table 1. The curve of Example '1' in Table 1 shows the case where 1.25% of E was added, and the curve of Control Example '21 shows the case where E was not added.

The results in Table 1 show that EBS and MSA not only improve the thermal stability of polyvinyl chloride compounds containing talc, but also that when the premixing time is increased, the impact strength of the control example decreases rapidly, whereas the amide of the present invention It can be seen that when compounds are included, they are less affected by premixing.

As can be seen from Table 1 and Table 1, the less ΔT, .DELTA.L decreases, the smaller the drop in impact strength is, and there is no direct relationship with the length of time for ΔT, .DELTA.L.

EBS is better than MSA when looking only at △T,,△T2 value, but when MSA is added with 1.25% talc, EBS is better than MSA.
．． The drop in impact strength is as small as when adding 75%.

Polyamide with a melting point of 20° or less has the effect of improving △T, △T2 in large quantities, but let's examine the effect of premixing on methanol-soluble nylon (trade name, Toyo Rayon, CM-8000). As shown in the comparative example in Table 1, the longer the premixing time is, the greater the drop in impact strength is.If the thermal stability is improved at 0 premixing, the drop in impact strength will always be small. It turns out there isn't.

Example 2 Talc having the particle size distribution shown in Table 2 was prepared by the method of Example 1.

10 or more 25.3% talc, 14.3% talc, 9.
A compound containing 15% talc is obtained using the formulation of Example 1 using 6% talc (same as in Example 1) and 4.8% talc.

As an example of the present invention, ΔT, ΔT2 DuPont was measured using 2.5% EBS to talc and premixing for 0 minutes and 10 minutes.

As a control example, a sample without E spots was similarly measured.
As shown in Table 3, no matter which talc is used, the E of the present invention
The influence of pre-mixing on ΔT, ΔT2 is small, and the spots are improved in comparison with the control example.

The same is true for DuPont, and it can be seen that in the present invention, even if premixed, there is almost no decrease. On the other hand, the DuPont value is greatly influenced by the particle size of the talc, and the smaller the number of particles of 10r or more, the higher the value.Practically speaking, particles of 10r or more need to be 15% or less, but in this case it is particularly noticeable. I can see that it is working.

Table 2 (Note) Shimadzu centrifugal sedimentation type particle size analyzer OP-50 used Solvent used: Distilled water Dispersant: 0.2% NaP02) 6 Measurement temperature 29°C Example 3 Premixed in the same manner as Example 1 for 0 minutes and make 10 compounds.

In this case, the compounds of the present invention include ethylene bisstearamide (MBS), methylene bispalmitic acid ad(
MBP), ethylene bispalmitic acid amide (EBP)
, ethylene bisoleic acid amide (EBO) was added at a concentration of 3.75% based on talc, and methylolated palmitic acid amide (MPA), methylolated behenic acid amide (M old A), and methylolated oleic acid were added. Amide (MOA)
were added in an amount of 1.25% based on talc, MSA was added at 1.25% based on talc, and CM-8000 (manufactured by Toyo Rayon Co., Ltd.) was added as a polyamide with a melting point (mp) of 200 qo or less at 1% based on talc. Similarly, in Example 1, when looking at the plastogram △T, △T2 and the DuPont measurement results for the molded product, it can be seen that the influence of preliminary loss is small in both cases, and the effects of the present invention are fully demonstrated. (Table 4). In the case of methylolated fatty acid amide △T,,
The value of △T2 itself has not been improved much, but when CM-8000 is used in combination with this, △T, and △T2 are each significantly improved. Also, CM-800 alone was easily affected by premixing, but when used in combination, It can be seen that the characteristics of both are exhibited. Furthermore, even if the talc content in the compound of the present invention is other than 15%, for example, when the talc content in the compound is measured and added to 1%, 10%, 20%, or 40%, the same applies. The effect of adding the amide compound of the invention was extremely large, and no major difference was observed from the case of the above example.

Table 4 Example 4 With the talc formulation of Example 1, the spar mixer and 10
△T, △L DuPont was measured using the same spar mixer according to the method of Example 1 (premixing time: 0 minutes).

As an example of the present invention, EBS was added to talc at 2.5% and M
SA to talc 1.25%, EBS to talc 2.5%,
Using the case where CM-8000 and 1% of talc were added,
As control examples, a case where no addition was made and a case where CM-8000 was added at 1% based on talc were used.

As shown in Table 5, when the mixer is used without addition of 100%, the DuPont strength decreases to medium and the thermal stability also deteriorates. When CM-8000 was added, the thermal stability was improved compared to when it was not added, but 1
00 Using that mixer, DuPont will be lower and △T
, , ΔT2 are both lower than when using a 20-so mixer. In the examples shown in Table 5, there is almost no difference between △T, △T2 and DuPont even if a 100 mm mixer is used.
It can be seen that stable physical properties can be obtained. Table 5

[Brief explanation of the drawing]

FIG. 1 shows plastograms when 1.25% of EBS described in Example 1 was added (Example) and when no EBS was added (Control example) at a premixing time of 0 minutes. The time showing the technical torque is TB (minutes), and the time 0.1k91m higher than the minimum torque is the one closest to the maximum torque (
Tc), with the far one being Tc, ΔT,=Tc-(Tc) ΔT2=Tc-TB d=0.1k91m. ΔT, is the steady torque holding time, and ΔT2 is the time from when the maximum torque is reached until the start of disassembly. 1... Example curve, 2... Control example curve. illustration ship

Claims (1)

[Claims] 1 An amide compound represented by R_1CONHR_2 and 1
A reinforced polyvinyl chloride resin composition characterized in that particles having a size of 0μ or more contain 15% or less of talc. However, R_1 is a saturated or unsaturated aliphatic hydrocarbon, and R_2
excludes H -CH_2OR_5 or -R_3NH-CO
R_4 (where R_3, R_4, and R_5 are each represented by H or the same or different saturated or unsaturated aliphatic hydrocarbons). 2 The amide compound represented by R_1CONHR_2 is 1
The reinforced polyvinyl chloride resin composition according to claim 1, wherein the particles having a size of 0 μ or more are present in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of 15% or less of talc. However, R_1 and R_2 are as described in Section 1. 3 Talc content of 15% or more with particles of 10μ or more is 1
Claim 1: % by weight or more and 40% by weight or less
The reinforced polyvinyl chloride resin composition according to item 1 or 2.